Herbicides

ABSTRACT

Cyclohexanedione compounds, which are suitable for use as herbicides.

This application is a 371 of International Application No.PCT/EP2009/062327 filed Sep. 23, 2009, which claims priority to GB0819205.6 filed Oct. 20, 2008, the contents of which are incorporatedherein by reference.

The present invention relates to novel, herbicidally active cyclicdiones, and derivatives thereof, to processes for their preparation, tocompositions comprising those compounds, and to their use in controllingweeds, especially in crops of useful plants, or in inhibiting plantgrowth.

Cyclic diones having herbicidal action are described, for example, in WO08/110,308.

Novel cyclohexanedione compounds having herbicidal and growth-inhibitingproperties have now been found.

The present invention accordingly relates to compounds of formula I

wherein

R¹ is methyl, ethyl, n-propyl, isopropyl, cyclopropyl, halomethyl,haloethyl, halogen, vinyl, ethynyl, methoxy, ethoxy, halomethoxy orhaloethoxy,

R² and R³ are, independently hydrogen, halogen, C₁-C₆alkyl,C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₂-C₆alkenyl,C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₃-C₆alkenyloxy, C₃-C₆haloalkenyloxy,C₃-C₆alkynyloxy, C₃-C₆cycloalkyl, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl,C₁-C₆alkylsulfonyl, C₁-C₆alkoxysulfonyl, C₁-C₆haloalkoxysulfonyl, cyano,nitro, phenyl, phenyl substituted by C₁-C₄ alkyl, C₁-C₃haloalkyl,C₁-C₃alkoxy, C₁-C₃alkoxy-C₁-C₃alkoxy, C₁-C₃haloalkoxy, aminocarbonyl,cyano, nitro, halogen, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl orC₁-C₃alkylsulfonyl, or phenyl wherein 2 adjacent carbon atoms arebridged by a —O—CH₂—O— or —O—CH₂—CH₂—O— group, or heteroaryl orheteroaryl substituted by C₁-C₄ alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,cyclopropyl-C₁-C₃alkoxy, C₁-C₃haloalkoxy, cyano, nitro, halogen,C₁-C₃alkylthio, C₁-C₃alkylsulfinyl or C₁-C₃alkylsulfonyl,

R⁴ is hydrogen, methyl, ethyl, n-propyl, isopropyl, halomethyl,haloethyl, halogen, vinyl, ethynyl, methoxy, ethoxy, halomethoxy orhaloethoxy,

R⁵ is hydrogen or methyl,

R⁶ and R⁷ are independently hydrogen, methyl, ethyl, C₃-C₆cycloalkyl,halogen, halomethyl, haloethyl, halogen, methoxy, halomethoxy,haloethoxy, or together R⁶ and R⁷ are joined to form together with thecarbon atom to which they are attached a 3-7 membered ring or a 3-7membered ring substituted by one or two methyl groups,

Q is a 3- to 8-membered saturated or mono-unsaturated heterocyclecontaining at least one heteroatom selected from O, N and S(O)_(p), or Qis a 3- to 8-membered saturated or mono-unsaturated heterocyclecontaining at least one heteroatom selected from O, N and S(O)_(p),which is substituted by ═O, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₄alkoxy-C₁-C₂ alkyl, C₃-C₆cycloalkyl or C₃-C₆cycloalkyl-C₁-C₃alkyl, or issubstituted by a 3- to 6-member heterocycyl containing at least oneheteroatom selected from O and N, or is substituted by a 3- to6-membered heterocyclyl-C₁-C₃alkyl containing at least one heteroatomselected from O and N, or is substituted by a spiro-C₃-C₆cycloalkyl or aspiro-3- to 8-membered saturated heterocycle containing at least oneheteroatom selected from O, N and S(O)_(p), or is bridged by a —O—CH₂—group, or Q is a 6- to 10-membered bicyclic heterocycle containing atleast one heteroatom selected from O, N and S(O)_(p), p is 0, 1 or 2,and

G is hydrogen, C₁-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, an alkali metal,alkaline earth metal, a sulfonium, ammonium or latentiating group.

In the substituent definitions of the compounds of the formula I, thealkyl substituents and alkyl moieties of alkoxy, alkylsulfonyl etc.having 1 to 6 carbon atoms are preferably methyl, ethyl as well aspropyl, butyl, pentyl and hexyl, in form of their straight and branchedisomers. The alkenyl and alkynyl radicals having 2 to 6 carbon atoms aswell as up to 10 carbon atoms can be straight or branched and cancontain more than 1 double or triple bond. Examples are vinyl, allyl,propargyl, butenyl, butynyl, pentenyl and pentynyl. Suitable cycloalkylgroups contain 3 to 7 carbon atoms and are for example cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl. Cyclopropyl,cyclobutyl, cyclopentyl and cyclohexyl are preferred. Preferred halogensare chlorine and bromine. Preferred examples of heteroaryls are thienyl,furyl, pyrrolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl,pyrazolyl, imidazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl,pyrazinyl, triazinyl, oxadiazolyl and thiadiazolyl, and, whereappropriate, N-oxides and salts thereof. These aryls and heteroaryls canbe substituted by one or more substituents, where preferred substituentsare C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, cyano,nitro, halogen, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl andC₁-C₃alkylsulfonyl. The 3-7 membered rings formed by R⁶ and R⁷ togetherwith the carbon atom to which they are attached are preferably saturatedand preferably carbocyclic rings which can be substituted by one or twomethyl groups. Examples of the preferred saturated or mono-unsaturatedrings Q can be found below as groups Q₁ to Q₈₅. The group G denoteshydrogen, an alkali metal cation such as sodium or potassium, alkalineearth metal cation such as calcium, sulfonium cation (preferably—S(C₁-C₆alkyl₃)⁺) or ammonium cation (preferably —NH₄ ⁺ or—N(C₁-C₆alkyl)₄ ⁺), or C₁-C₆alkyl, C₃-C₆alkenyl or C₃-C₆alkynyl or alatentiating group. The latentiating group G is preferably selected fromthe groups —C(X¹)—R⁶, C(X²)—X³—R⁷, —C(X⁴)—NR⁸R⁹, —SO₂R¹⁰, P(X⁵)R¹¹R¹² orCH₂—X⁶—R¹³, wherein X¹, X², X³, X⁴, X⁵ and X⁶ are independently of eachother oxygen or sulfur;

R⁶, R⁷, R⁸ and R⁹ are each independently of each other hydrogen, C₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₁-C₁₀haloalkyl, C₁-C₁₀cyanoalkyl,C₁-C₁₀nitroalkyl, C₁-C₁₀aminoalkyl, C₁-C₅-aminoalkylC₁-C₅alkyl,C₂-C₈dialkylaminoC₁-C₅alkyl, C₃-C₇cycloalkylC₁-C₅alkyl,C₂-C₁₀alkoxyalkyl, C₄-C₁₀alkenyloxyalkyl, C₄-C₁₀alkynyloxyalkyl,C₂-C₁₀alkylthioalkyl, C₁-C₅alkylsulfinylC₁-C₅alkyl,C₁-C₅alkylsulfonylC₁-C₅alkyl, C₂-C₈alkylideneaminoxoyC₁-C₅alkyl,C₁-C₅alkylcarbonylC₁-C₅alkyl, C₁-C₅alkoxycarbonylC₁-C₅alkyl,C₁-C₅alkylaminocarbonylC₁-C₅alkyl, C₂-C₈dialkylaminocarbonylC₁-C₅alkyl,C₁-C₅alkylcarbonylaminoC₁-C₅alkyl,N—C₁-C₅alkylcarbonyl-N—C₂-C₅alkylaminoalkyl,C₃-C₆trialkylsilylC₁-C₅alkyl, phenylC₁-C₅alkyl, heteroarylC₁-C₅alkyl,C₂-C₅alkenyl, C₂-C₅haloalkenyl, C₃-C₈cycloalkyl, phenyl or phenylsubstituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy,halogen, cyano or nitro, or heteroaryl or heteroarylamino substituted byC₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyanoor nitro, diheteroarylamino or diheteroarylamino substituted byC₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyanoor nitro, phenylamino or phenylamino substituted by C₁-C₃alkyl,C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or bynitro, diphenylamino or diphenylamino substituted by C₁-C₃alkyl,C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or by nitroor C₃-C₇cycloalkylamino, di-C₃-C₇cycloalkylamino or C₃-C₇cycloalkoxy,

R¹⁰, R¹¹, R¹² are hydrogen, C₁-C₁₀ alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl,C₁-C₁₀haloalkyl, C₁-C₁₀cyanoalkyl, C₁-C₁₀nitroalkyl, C₁-C₁₀aminoalkyl,C₁-C₅ aminoalkylC₁-C₅alkyl, C₂-C₅dialkylaminoC₁-C₅alkyl,C₃-C₇cycloalkylC₁-C₅alkyl, C₂-C₁₀alkoxyalkyl, C₄-C₁₀alkenyloxyalkyl,C₄-C₁₀alkynyloxyalkyl, C₂-C₁₀alkylthioalkyl,C₁-C₅alkylsulfinylC₁-C₅alkyl, C₁-C₅alkylsulfonylC₁-C₅alkyl,C₂-C₈alkylideneaminoxoyC₁-C₅alkyl, C₁-C₅alkylcarbonylC₁-C₅alkyl,C₁-C₅alkoxycarbonylC₁-C₅alkyl, C₁-C₅aminocarbonylC₁-C₅alkyl,C₂-C₈dialkylaminocarbonylC₁-C₅alkyl, C₁-C₅alkylcarbonylaminoC₁-C₅alkyl,N—C₁-C₅alkylcarbonyl-N—C₂-C₅alkylaminoalkyl,C₃-C₆trialkylsilylC₁-C₅alkyl, phenylC₁-C₅alkyl, heteroarylC₁-C₅alkyl,C₂-C₅alkenyl, C₂-C₅haloalkenyl, C₃-C₈cycloalkyl, phenyl or phenylsubstituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy,halogen, cyano or nitro, heteroaryl or heteroarylamino substituted byC₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyanoor by nitro, diheteroarylamino or diheteroarylamino substituted byC₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyanoor nitro, phenylamino or phenylamino substituted by C₁-C₃alkyl,C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or nitro,diphenylamino, or diphenylamino substituted by C₁-C₃alkyl,C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or nitro,or C₃-C₇cycloalkylamino, diC₃-C₇cycloalkylamino or C₃-C₇cycloalkoxy,C₁-C₁₀alkoxy, C₁-C₁₀haloalkoxy, C₁-C₅alkylamino, C₂-C₈dialkylamino,benzyloxy or phenoxy, wherein the benzyl and phenyl groups may in turnbe substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,C₁-C₃haloalkoxy, halogen, cyano or nitro, and

R¹³ is C₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₁-C₁₀haloalkyl,C₁-C₁₀cyanoalkyl, C₁-C₁₀nitroalkyl, C₁-C₁₀aminoalkyl,C₁-C₅aminoalkylC₁-C₅alkyl, C₂-C₈dialkylaminoC₁-C₅alkyl,C₃-C₇cycloalkylC₁-C₅alkyl, C₂-C₁₀alkoxyalkyl, C₄-C₁₀alkenyloxyalkyl,C₄-C₁₀alkynyloxyalkyl, C₂-C₁₀alkylthioalkyl,C₁-C₅alkylsulfinylC₁-C₅alkyl, C₁-C₅alkylsulfonylC₁-C₅alkyl, C₂-C₈alkylideneaminoxoyC₁-C₅alkyl, C₁-C₅alkylcarbonylC₁-C₅alkyl,C₁-C₅alkoxycarbonylC₁-C₅alkyl, C₁-C₅aminocarbonylC₁-C₅alkyl,C₂-C₈dialkylaminocarbonylC₁-C₅alkyl, C₁-C₅alkylcarbonylaminoC₁-C₅alkyl,N—C₁-C₅alkylcarbonyl-N—C₂-C₅alkylaminoalkyl, C₃-C₆trialkylsilylC₁-C₅alkyl, phenylC₁-C₅alkyl, heteroarylC₁-C₅alkyl,phenoxyC₁-C₅alkyl, heteroaryloxyC₁-C₅alkyl, C₂-C₅alkenyl,C₂-C₅haloalkenyl, C₃-C₈cycloalkyl, phenyl or phenyl substituted byC₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen or bynitro, or heteroaryl or heteroarylamino, or heteroaryl orheteroarylamino substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,C₁-C₃haloalkoxy, halogen, cyano or by nitro, or heteroaryl orheteroarylamino, or heteroaryl or heteroarylamino substituted byC₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyanoor by nitro, diheteroarylamino or diheteroarylamino substituted byC₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyanoor by nitro, phenylamino, or phenylamino substituted by C₁-C₃alkyl,C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or bynitro, diphenylamino, or diphenylamino substituted by C₁-C₃alkyl,C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or bynitro, or C₃-C₇cycloalkylamino, diC₃-C₇cycloalkylamino orC₃-C₇cycloalkoxy or C₁-C₁₀alkylcarbonyl.

In particular, the latentiating group G is a group —C(X¹)—R⁶ or—C(X²)—X³—R⁷, and the meanings of X¹, R⁶, X², X³ and R⁷ are as definedabove.

These latentiating groups G are selected to allow its removal by one ora combination of biochemical, chemical or physical processes to affordcompounds of formula I where G is H before, during or followingapplication to the treated area or plants. Examples of these processesinclude enzymatic cleavage, chemical hydrolysis and photoloysis.Compounds bearing such groups G may offer certain advantages, such asimproved penetration of the cuticula of the plants treated, increasedtolerance of crops, improved compatibility or stability in formulatedmixtures containing other herbicides, herbicide safeners, plant growthregulators, fungicides or insecticides, or reduced leaching in soils.

In a preferred group of compounds of the formula I, R¹ is methyl, ethyl,cyclopropyl or methoxy.

Preferably, R² and R³ in the compounds of formula I are independentlyhydrogen, halogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy,C₁-C₆haloalkoxy, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl,C₃-C₆alkenyloxy, C₃-C₆haloalkenyloxy, C₃-C₆alkynyloxy, C₃-C₆cycloalkyl,C₁-C₆alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl,C₁-C₆alkoxysulfonyl, C₁-C₆haloalkoxysulfonyl, cyano, nitro, phenyl,phenyl substituted by C₁-C₄alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,C₁-C₃haloalkoxy, cyano, nitro, halogen, C₁-C₃alkylthio,C₁-C₃alkylsulfinyl or C₁-C₃alkylsulfonyl, or thienyl, thienylsubstituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy,cyano, nitro, halogen, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl orC₁-C₃alkylsulfonyl, furyl, furyl substituted by C₁-C₃alkyl,C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, cyano, nitro, halogen,C₁-C₃alkylthio, C₁-C₃alkylsulfinyl or C₁-C₃alkylsulfonyl, pyrazolyl,pyrazolyl substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,C₁-C₃haloalkoxy, cyano, nitro, halogen, C₁-C₃alkylthio,C₁-C₃alkylsulfinyl or C₁-C₃alkylsulfonyl, thiazolyl, thiazolylsubstituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy,cyano, nitro, halogen, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl orC₁-C₃alkylsulfonyl, oxazolyl, oxazolyl substituted by C₁-C₃alkyl,C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, cyano, nitro, halogen,C₁-C₃alkylthio, C₁-C₃alkylsulfinyl or C₁-C₃alkylsulfonyl, isothiazolyl,isothiazolyl substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,C₁-C₃haloalkoxy, cyano, nitro, halogen, C₁-C₃alkylthio,C₁-C₃alkylsulfinyl or C₁-C₃alkylsulfonyl, isoxazolyl, isoxazolylsubstituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy,cyano, nitro, halogen, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl orC₁-C₃alkylsulfonyl, triazolyl, triazolyl substituted by C₁-C₃alkyl,C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, cyano, nitro, halogen,C₁-C₃alkylthio, C₁-C₃alkylsulfinyl or C₁-C₃alkylsulfonyl, oxadiazolyl,oxadiazolyl substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,C₁-C₃haloalkoxy, cyano, nitro, halogen, C₁-C₃alkylthio,C₁-C₃alkylsulfinyl or C₁-C₃alkylsulfonyl, thiadiazolyl, thiadiazolylsubstituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy,cyano, nitro, halogen, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl orC₁-C₃alkylsulfonyl, tetrazolyl, tetrazolyl substituted by C₁-C₃alkyl,C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, cyano, nitro, halogen,C₁-C₃alkylthio, C₁-C₃alkylsulfinyl or C₁-C₃alkylsulfonyl, pyridyl,pyridyl substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,C₁-C₃haloalkoxy, cyano, nitro, halogen, C₁-C₃alkylthio,C₁-C₃alkylsulfinyl or C₁-C₃alkylsulfonyl, pyrimidinyl, pyrimidinylsubstituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy,cyano, nitro, halogen, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl orC₁-C₃alkylsulfonyl, pyridazinyl, pyridazinyl substituted by C₁-C₃alkyl,C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, cyano, nitro, halogen,C₁-C₃alkylthio, C₁-C₃alkylsulfinyl or C₁-C₃alkylsulfonyl, pyrazinyl orpyrazinyl substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,C₁-C₃haloalkoxy, cyano, nitro, halogen, C₁-C₃alkylthio,C₁-C₃alkylsulfinyl or C₁-C₃alkylsulfonyl, triazinyl or triazinylsubstituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy,cyano, nitro, halogen, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl orC₁-C₃alkylsulfonyl,

More preferably, R² and R³ are independently hydrogen, halogen,C₁-C₆alkyl, C₁-C₆alkoxy, C₂-C₆alkenyl, C₂-C₆alkynyl, phenyl or phenylsubstituted by C₁-C₄alkyl, C₁-C₃haloalkyl, cyano, nitro, halogen orC₁-C₃alkylsulfonyl.

In even more preferred compounds of the formula I, R² and R³ areindependently hydrogen, chlorine, bromine, methyl, methoxy, ethyl,ethoxy, ethenyl, ethynyl, phenyl or phenyl substituted by methyl,trifluoromethyl, cyano, nitro, fluorine, chlorine or methylsulfonyl.

Preferably, R⁴ is hydrogen, methyl, ethyl, chlorine, bromine, vinyl,ethynyl or methoxy.

Preferred are those compounds of the formula I, wherein R⁵ is hydrogen.

In another preferred group of the compounds of the formula I one of R⁶and R⁷ are hydrogen.

It is also preferred that R⁶ and R⁷ are both hydrogen.

Preferably, G denotes hydrogen, an alkali metal or alkaline earth metal,where hydrogen is particularly preferred.

Preferred groups Q are those of the formula

wherein R is C₁₋₄ alkyl, C₁₋₄ haloalkyl, C₁₋₄ alkoxy C₁₋₂ alkyl or C₃₋₆cycloalkyl, n is 0 to 4 and -A denotes the position of attachment to themethylene moiety —CR⁵R⁶—.

Groups Q₁, Q₂, Q₅, Q₆, Q₇, Q₂₅, Q₂₆, Q₂₇, Q₂₈, Q₂₉, Q₃₄, Q₄₂ and Q₄₃ areeven more preferred, where Groups, Q₂, Q₇, Q₂₅, Q₂₇, Q₃₄, Q₄₂ and Q₄₃are especially preferred.

Preferably, R is methyl or ethyl.

0, 1 and 2 are the preferred meanings of n.

In another group of preferred compounds of the formula I, Q is a 6- to10-membered bicyclic heterocycle such as Q₇₃ and Q₈₆, especially Q₈₆.

In a particularly preferred group of compounds of the formula I, R¹ ismethyl, ethyl or methoxy, R² and R³ are independently hydrogen, halogen,C₁-C₆alkyl, phenyl, phenyl substituted by C₁-C₄alkyl, C₁-C₃haloalkyl,C₁-C₃alkoxy, C₁-C₃alkoxy-C₁-C₃alkoxy, C₁-C₃haloalkoxy, aminocarbonyl,cyano or halogen, or phenyl wherein 2 adjacent carbon atoms are bridgedby a —O—CH₂—O— or —O—CH₂—CH₂—O— group, or heteroaryl or heteroarylsubstituted by C₁-C₃alkoxy or cyclopropyl-C₁-C₃alkoxy,

R⁴ is hydrogen, methyl or ethyl,

R⁵ is hydrogen,

R⁶ and R⁷ are independently hydrogen or methyl,

Q is a 5- to 7-membered saturated heterocycle containing at least oneheteroatom selected from O and S(O)_(p), or Q is a 5- to 7-memberedsaturated or mono-unsaturated heterocycle containing at least oneheteroatom selected from O and S(O)_(p), which is substituted byC₁-C₄alkyl or C₁-C₄alkoxy-C₁-C₂alkyl, or is substituted by a 5- to6-membered heterocycyl containing at least one O atom, or is substitutedby a 5- to 6-membered heterocyclyl-C₁-C₃alkyl containing at least one Oatom, or is substituted by a spiro-C₃-C₆cycloalkyl or a spiro-5- to6-membered saturated heterocycle containing at least one O atom, or Q isa 8- to 10-membered bicyclic heterocycle containing at least one O atom,

p is 0, 1 or 2, and

G is hydrogen.

The invention relates also to the salts which the compounds of formula Iare able to form with amines, alkali metal and alkaline earth metalbases or quaternary ammonium bases.

Among the alkali metal and alkaline earth metal hydroxides as saltformers, special mention should be made of the hydroxides of lithium,sodium, potassium, magnesium and calcium, but especially the hydroxidesof sodium and potassium. The compounds of formula I according to theinvention also include hydrates which may be formed during the saltformation.

Examples of amines suitable for ammonium salt formation include ammoniaas well as primary, secondary and tertiary C₁-C₁₈alkylamines,C₁-C₄hydroxyalkylamines and C₂-C₄alkoxyalkylamines, for examplemethylamine, ethylamine, n-propylamine, isopropylamine, the fourbutylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine,octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine,heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine,methylhexylamine, methylnonylamine, methylpentadecylamine,methyloctadecylamine, ethylbutylamine, ethylheptylamine,ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine,diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine,di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine,dioctylamine, ethanolamine, n-propanolamine, isopropanolamine,N,N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine,allylamine, n-but-2-enylamine, n-pent-2-enylamine,2,3-dimethylbut-2-enylamine, dibut-2-enylamine, n-hex-2-enylamine,propylenediamine, trimethylamine, triethylamine, tri-n-propylamine,triisopropylamine, tri-n-butylamine, triisobutylamine,tri-sec-butylamine, tri-n-amylamine, methoxyethylamine andethoxyethylamine; heterocyclic amines, for example pyridine, quinoline,isoquinoline, morpholine, piperidine, pyrrolidine, indoline,quinuclidine and azepine; primary arylamines, for example anilines,methoxyanilines, ethoxyanilines, o-, m- and p-toluidines,phenylenediamines, benzidines, naphthylamines and o-, m- andp-chloroanilines; but especially triethylamine, isopropylamine anddiisopropylamine.

Preferred quaternary ammonium bases suitable for salt formationcorrespond, for example, to the formula [N(R_(a)R_(b)R_(c)R_(d))]OHwherein R_(a), R_(b), R_(c) and R_(d) are each independently of theothers C₁-C₄ alkyl. Further suitable tetraalkylammonium bases with otheranions can be obtained, for example, by anion exchange reactions.

Depending on the nature of the substituents, compounds of formula I mayexist in different isomeric forms. When G is hydrogen, for example,compounds of formula I may exist in different tautomeric forms. Thisinvention covers all such isomers and tautomers and mixtures thereof inall proportions. Also, when substituents contain double bonds, cis- andtrans-isomers can exist. These isomers, too, are within the scope of theclaimed compounds of the formula I.

A compound of formula I wherein G is C₁-C₈ alkyl, C₃-C₈ alkenyl, C₃-C₈alkynyl, C(X¹)—R²⁰, C(X²)—X³—R²¹, C(X⁴)—N(R²²)—R²³, —SO₂—R²⁴,—P(X⁵)(R²⁵)—R²⁶ or CH₂—X—R²⁷ where X¹, X², X³, X⁴, X⁵, X, R²⁰, R²¹, R²²,R²³, R²⁴, R²⁵, R²⁶ and R²⁷ are as defined above may be prepared bytreating a compound of Formula (A), which is a compound of formula Iwherein G is H, with an alkylating agent such as an alkyl halide (thedefinition of alkyl halides includes simple alkyl halides such as methyliodide and ethyl iodide and substituted alkyl halides such aschloromethyl alkyl ethers, Cl—CH₂—X—R²⁷, wherein X is oxygen, andchloromethyl alkyl sulfides Cl—S—CH₂—X—R²⁷, wherein X is sulfur), analkyl sulfonate, or a dialkyl sulfate, or with an alkenyl halide, orwith an alkynyl halide, or with an acylating agent such as a carboxylicacid, HO—C(X¹)R²⁰, wherein X¹ is oxygen, an acid chloride, Cl—C(X¹)R²⁰,wherein X¹ is oxygen, or acid anhydride, [R²⁰C(X¹)]₂₀, wherein X¹ isoxygen, or an isocyanate, R²²N═C═O, or a carbamoyl chloride,Cl—C(X⁴)—N(R²²)—R²³ (wherein X⁴ is oxygen and with the proviso thatneither R²² or R²³ is hydrogen), or a thiocarbamoyl chloride,Cl—C(X⁴)—N(R²²)—R²³ (wherein X⁴ is sulfur and with the proviso thatneither R²² or R²³ is hydrogen) or a chloroformate, Cl—C(X²)—X³—R²¹,(wherein X² and X³ are oxygen), or a chlorothioformate Cl—C(X²)—X³—R²¹(wherein X² is oxygen and X³ is sulfur), or an isothiocyanate, R²²N═C═S,or by sequential treatment with carbon disulfide and an alkylatingagent, or with a phosphorylating agent such as a phosphoryl chloride,Cl—P(X⁵)(R²⁵)—R²⁶ or with a sulfonylating agent such as a sulfonylchloride C₁—SO₂—R²⁴, preferably in the presence of at least oneequivalent of base.

The O-alkylation of cyclic 1,3-diones is known; suitable methods aredescribed, for example, in U.S. Pat. No. 4,436,666. Alternativeprocedures have been reported by M. T. Pizzorno and S. M. Albonico,Chem. Ind. (London), 1972, 425; H. Born et al., J. Chem. Soc., 1953,1779; M. G. Constantion et al., Synth. Commun., 1992, 22 (19), 2859; Y.Tian et al., Synth. Commun., 1997, 27 (9), 1577 and by S. Chandra Roy etal., Chem. Letters, 2006, 35, (No 1) 16.

The acylation of 2-arylcycloxane-3,5-diones may be effected byprocedures similar to those described, for example, in U.S. Pat. No.4,175,135, U.S. Pat. No. 4,422,870, U.S. Pat. No. 4,659,372 and U.S.Pat. No. 4,436,666. Typically diones of Formula (A) are treated with theacylating agent in the presence of at least one equivalent of a suitablebase, optionally in the presence of a suitable solvent. The base may beinorganic, such as an alkali metal carbonate or hydroxide, or a metalhydride, or an organic base such as a tertiary amine or metal alkoxide.Examples of suitable inorganic bases include sodium carbonate, sodium orpotassium hydroxide, sodium hydride, and suitable organic bases includetrialkylamines, such as trimethylamine and triethylamine, pyridines orother amine bases such as 1,4-diazobicyclo[2.2.2]octane and1,8-diazabicyclo[5.4.0]undec-7-ene. Preferred bases includetriethylamine and pyridine. Suitable solvents for this reaction areselected to be compatible with the reagents and include ethers such astetrahydrofuran and 1,2-dimethoxyethane and halogenated solvents such asdichloromethane and chloroform. Certain bases, such as pyridine andtriethylamine, may be employed successfully as both base and solvent.For cases where the acylating agent is a carboxylic acid, acylation ispreferably effected in the presence of a coupling agent such as2-chloro-1-methylpyridinium iodide, N,N′-dicyclohexycarbodiimide,1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and N,N′-carbodiimidazole,and a base such as triethylamine or pyridine in a suitable solvent suchas tetrahydrofuran, dichloromethane or acetonitrile. Suitable proceduresare described, for example, by W. Zhang and G. Pugh, Tetrahedron Lett.,1999, 40 (43), 7595-7598 and T. Isobe and T. Ishikawa, J. Org. Chem.,1999, 64 (19) 6984.

Phosphorylation of 2-arylcyclohexane-3,5-diones may be effected usingprocedures analogous to those described in U.S. Pat. No. 4,409,153.

Sulfonylation of a compound of Formula (A) may be achieved using analkyl or aryl sulfonyl halide, preferably in the presence of at leastone equivalent of base, for example by the procedure of C. J. Kowalskiand K. W. Fields, J. Org. Chem., 1981, 46, 197.

A compound of Formula (A) may be prepared via the cyclisation of acompound of Formula (B), wherein R is hydrogen or an alkyl group,preferably in the presence of an acid or base, and optionally in thepresence of a suitable solvent, by analogous methods to those describedin U.S. Pat. No. 4,209,532. The compounds of Formula (B) have beenparticularly designed as intermediates in the synthesis of the compoundsof the Formula I. A compound of Formula (B) wherein R is hydrogen may becyclised under acidic conditions, preferably in the presence of a strongacid such as sulfuric acid, polyphosphoric acid or Eaton's reagent,optionally in the presence of a suitable solvent such as acetic acid,toluene or dichloromethane.

A compound of Formula (B) wherein R is alkyl (preferably methyl orethyl), may be cyclised under basic conditions, preferably in thepresence of at least one equivalent of a strong base such as potassiumtert-butoxide, lithium diisopropylamide or sodium hydride and in asolvent such as tetrahydrofuran, dimethylsulfoxide orN,N-dimethylformamide.

A compound of Formula (B), wherein R is H, may be prepared bysaponification of a compound of Formula (C) wherein R′ is alkyl(preferably methyl or ethyl), under standard conditions, followed byacidification of the reaction mixture to effect decarboxylation, bysimilar processes to those described, for example, in U.S. Pat. No.4,209,532.

A compound of Formula (B), wherein R is H, may be esterified to acompound of Formula (B), wherein R is alkyl, under known conditions, forexample by heating with an alkyl alcohol, ROH, in the presence of anacid catalyst.

A compound of Formula (C), wherein R is alkyl, may be prepared bytreating a compound of Formula (D) with a suitable carboxylic acidchloride of Formula (E) wherein under basic conditions. Suitable basesinclude potassium tert-butoxide, sodium bis(trimethylsilyl)amide andlithium diisopropylamide and the reaction is preferably conducted in asuitable solvent (such as tetrahydrofuran or toluene) at a temperatureof between −80° C. and 30° C. Alternatively, a compound of Formula (C),wherein R is H, may be prepared by treating a compound of Formula (D)with a suitable base (such as potassium tert-butoxide, sodiumbis(trimethylsilyl)amide and lithium diisopropylamide) in a suitablesolvent (such as tetrahydrofuran or toluene) at a suitable temperature(between −80° C. and 0° C.) and reacting the resulting anion with asuitable anhydride of Formula (F):

Compounds of Formula (D) are known compounds, or may be prepared fromknown compounds by known methods.

A compound of Formula (E) may be prepared from a compound of Formula (F)by treatment with an alcohol, R—OH, followed by treatment of theresulting acid with a chlorinating reagent such as oxalyl chloride orthionyl chloride under known conditions (see, for example, C. S.Rouvier. Tetrahedron Lett., 1984, 25, (39), 4371; D. M. Walba and M. D.Wand, Tetrahedron Lett., 1982, 23, 4995; J. Cason, Org. Synth. Coll.Vol. III, 169, 1955).

A compound of Formula (F) may be prepared by treating a compound ofFormula (G) with a dehydrating agent such as an acid anhydride (asdescribed, for example by J. Cason, Org. Synth. Coll. Vol. IV, 630,1963). A preferred acid anhydride is acetic anhydride.

A compound of Formula (G) may be prepared by hydrolysis of a ester ofFormula (H), wherein R″ and R′″ are suitable alkyl groups followed bydecarboxylation of resulting acid. Suitable alkyl groups are C₁-C₆alkyl,especially methyl or ethyl. Suitable methods for effecting hydrolysisare known, and include, for example, treating an ester of Formula (H)with an aqueous solution of a suitable base such as sodium hydroxide orlithium hydroxide, and acidifying the reaction mixture with an acid suchas hydrochloric acid to promote decarboxylation.

A compound of Formula (H) may be prepared by reacting a compound ofFormula (J) with a dialkyl malonate, such as dimethyl malonate ordiethyl malonate, under basic conditions. Preferred bases include sodiumalkoxide bases such as sodium methoxide and sodium ethoxide, and thereaction is preferably carried out in a solvent such as methanol,ethanol or toluene.

Compounds of Formula J are known compounds, or may be prepared fromknown compounds by known methods.

A compound of Formula (B) wherein R and R⁵ are both H may also beprepared via the hydrolysis and decarboxylation of a compound of Formula(K), which in turn is prepared by addition of a dialkyl malonate(preferably dimethyl malonate or diethyl malonate) to a compound ofFormula (L) in the presence of a suitable base, such as sodium methoxideor sodium ethoxide in a suitable solvent such as methanol, ethanol ortoluene. A compound of Formula (L) may be prepared by the Knoevenagelcondensation of an aldehyde of Formula (M) with a 3-ketoester of Formula(N) according to known procedures. A compound of Formula N may beprepared from a compound of Formula (D), wherein R is H, throughconversion to the corresponding acid chloride and subsequent reaction togive the β-ketoester of Formula (N) according to procedures described inthe literature (see, for example, J. Wemple et al., Synthesis, 1993,290-292; J. Bowman, J. Chem. Soc., 1950, 322).

Compounds of Formula (M) are known compounds, or may be prepared fromknown compounds by known methods.

Additional compounds of Formula (A) may be prepared by reacting a2-diazocyclo-hexane-1,3-dione of Formula (O) with a compound of Formula(P) under known conditions. Suitable procedures include thephotosensitised decomposition of diazoketones (see, for example, T. N.Wheeler, J. Org. Chem., 44, 4906, 1979), or by using a suitable metalcatalyst such as rhodium acetate, copper chloride or copper triflate ina suitable solvent under known conditions (see, for example, M. Oda etal., Chem. Lett. 1263, 1987). Where compounds of Formula (P) are liquidsat room temperature, these reactions may be effected in the absence ofany solvent. Compounds of Formula P are known, or may be prepared fromknown compounds by known methods.

A compound of Formula (O) may be prepared through treatment of acompound of Formula (Q) with a diazo transfer reagent such as tosylazide or mesyl azide and a base, as described, for example, by T. Ye andM. A. McKervey (Chem. Rev., 1994, 94, 1091-1160), by H. Stetter and K.Kiehs (Chem. Ber., 98, 1181, 1965) and by D. F. Taber et al. (J. Org.Chem., 1986, 51, 4077).

The compounds of the formula (Q) have been specifically designed asintermediates for the synthesis of the compounds of the formula (I).

A compound of Formula (Q) may be prepared via the hydrolysis anddecarboxylation of a compound of Formula (R), wherein R is alkyl, underknown conditions. Preferably R″″ is methyl or ethyl.

A compound of Formula (R) may be prepared by reacting a compound ofFormula (S) with a dialkyl malonate under basic conditions. Preferablythe dialkyl malonate is dimethyl malonate or diethyl malonate, the baseis a metal alkoxide such as sodium methoxide or sodium ethoxide and thereaction is carried out in a suitable solvent such as methanol, ethanolor toluene.

Compounds of Formula (S) are known, or may be prepared by known methodsfrom known compounds.

Additional compounds of Formula (Q), wherein R⁵ is H, may be preparedvia the reduction of compounds of Formula (T), followed by acidcatalysed hydrolysis of the resulting enol ethers of Formula (U). Apreferred method for effecting the reduction of a compound of Formula(T) is through the use of an alkali metal (such as lithium or sodium) ina suitable amine solvent (such as ammonia), and in the presence of analcohol, (such as methanol, ethanol or tert-butanol) according toprocedures described by, for example, E. M. Kaiser (Synthesis, 1972,391, and references therein) and by C. F. Masauger and E Ravina(Tetrahedron Lett., 1996, 37 (No 29), 5171.

A compound of Formula (T), wherein R⁷ is hydrogen, may be prepared bythe reduction of a compound of Formula (V) under known conditions, forexample by catalytic hydrogenation. A compound of Formula (V) may bealso be converted to a compound of Formula (U), wherein R⁷ is hydrogen,using an alkali metal (such as lithium or sodium) in a suitable aminesolvent (such as ammonia), and in the presence of an alcohol (such asmethanol or ethanol).

A compound of Formula (V) may be prepared by the addition of a Grignardreagent of Formula (W) wherein Hal is chlorine, bromine or iodine to acompound of Formula (X) in a suitable solvent. Preferably the Grignardreagent is 3,5-dimethoxyphenylmagnesium chloride and the solvent istetrahydrofuran or diethyl ether.

A compound of Formula (V) may also be prepared by reacting anorgano-lithium compound, Q-Li, or an organo-magnesium reagent, Q-Mg-Hal(where Hal is chlorine, bromine or iodine), with a compound of Formula(Y) in a suitable solvent such as tetrahydrofuran or diethyl ether.

Compounds of Formula (X) and compounds of Formula (Y) are knowncompounds, or may be prepared from known compounds by known method

A compound of Formula (T), wherein R⁷ is hydrogen, may also be preparedby the reduction of a styrene of Formula (Z) wherein A¹ and A² togetherform a suitable heterocyclic ring. A preferred method for reducing thestyrene is by hydrogenation over a suitable palladium catalyst underknown conditions.

A compound of Formula (U), wherein R⁷ is H, may also be prepared from acompound of Formula (Z) by reduction by an alkali metal (preferablylithium or sodium) in a suitable amine solvent, preferably ammonia, inthe presence of an alcohol such as methanol, ethanol or tert-butanol.

A compound of Formula (Z) may be prepared by the dehydration of acompound of Formula (AA), preferably under acidic conditions. A compoundof Formula (AA) may be prepared by reacting a compound of Formula (AB)with a Grignard reagent of Formula (W) wherein Hal is chlorine, bromineor iodine (and is preferably chlorine) in a suitable solvent such asdiethyl ether or tetrahydrofuran.

Compounds of Formula (AB) are known compounds, or may be prepared fromknown compounds by known methods.

A compound of Formula (Z) wherein R⁶ is hydrogen, may also be preparedby the reaction between a compound of Formula (AC), and a phosphonate ofFormula (AD) wherein R′″″ is alkyl (preferably methyl or ethyl) in thepresence of a suitable base such as sodium hydride, lithiumhexamethylsilazide, or n-butyl lithium and a suitable solvent such astetrahydrofuran or toluene.

Further compounds of Formula (AB) may be prepared by reacting a Grignardreagent of Formula (AE) wherein Hal is chlorine, bromine or iodine, witha compound of Formula AC, in a suitable solvent such as tetrahydrofuranor diethyl ether, followed by dehydration of the resulting alcohol ofFormula (AF).

Compounds of Formula (AC), compounds of Formula (AD) and compounds ofFormula (AE) are known compounds, or may be prepared from knowncompounds by known methods.

Additional compounds of Formula (A) may be prepared by reacting aniodonium ylide of Formula (AG), wherein Ar is an optionally substitutedphenyl group, and an aryl boronic acid of Formula (AH) in the presenceof a suitable palladium catalyst, a base and in a suitable solvent.

Suitable palladium catalysts are generally palladium(II) or palladium(0)complexes, for example palladium(II) dihalides, palladium(II) acetate,palladium(II) sulfate, bis(triphenylphosphine)palladium(II) dichloride,bis(tricyclopentylphosphine)palladium(II) dichloride,bis(tricyclohexyl-phosphine)palladium(II) dichloride,bis(dibenzylideneacetone)palladium(0) ortetrakis(triphenylphosphine)palladium(0). The palladium catalyst canalso be prepared “in situ” from palladium(II) or palladium(0) compoundsby complexing with the desired ligands, by, for example, combining thepalladium(II) salt to be complexed, for example palladium(II) dichloride(PdCl₂) or palladium(II) acetate (Pd(OAc)₂), together with the desiredligand, for example triphenylphosphine (PPh₃), tricyclopentylphosphineor tricyclohexylphosphine and the selected solvent, with a compound ofFormula (AG), the arylboronic acid of Formula (AH), and a base. Alsosuitable are bidendate ligands, for example1,1′-bis(diphenylphosphino)ferrocene or1,2-bis(diphenylphosphino)ethane. By heating the reaction medium, thepalladium(II) complex or palladium(0) complex desired for the C-Ccoupling reaction is thus formed “in situ”, and then initiates the C-Ccoupling reaction.

The palladium catalysts are used in an amount of from 0.001 to 50 mol %,preferably in an amount of from 0.1 to 15 mol %, based on the compoundof Formula (AG). The reaction may also be carried out in the presence ofother additives, such as tetralkylammonium salts, for example,tetrabutylammonium bromide. Preferably the palladium catalyst ispalladium acetate, the base is lithium hydroxide and the solvent isaqueous 1,2-dimethoxyethane.

A compound of Formula (AG) may be prepared from a compound of Formula(Q) by treatment with (diacetoxy)iodobenzene and a base such as aqueoussodium carbonate, lithium hydroxide or sodium hydroxide in a solventsuch as water or an aqueous alcohol such as aqueous ethanol according tothe procedures of K Schank and C Lick, Synthesis, 392 (1983), or of ZYang et al., Org. Lett., 2002, 4 (no 19), 3333:

An aryl boronic acid of Formula (AH) may be prepared from an aryl halideof Formula (AJ), wherein Hal is bromine or iodine, by known methods(see, for example, W. J. Thompson and J. Gaudino, J. Org. Chem., 1984,49, 5237 and R. T. Hawkins et al., J. Am. Chem. Soc., 1960, 82, 3053).For example, an aryl halide of Formula (AJ) may be treated with an alkyllithium or alkyl magnesium halide in a suitable solvent, preferablydiethyl ether or tetrahydrofuran, at a temperature of between −80° C.and 30° C., and the aryl magnesium or aryl lithium reagent obtained isthen reacted with a trialkyl borate (preferably trimethylborate) to givean aryl dialkylboronate which may be hydrolysed to the desired boronicacid of Formula (AH) under acidic conditions.

Aryl halides of Formula (AJ) may be prepared from anilines of Formula(AK) by known methods, for example the Sandmeyer reaction, via thecorresponding diazonium salts.

Anilines of Formula (AK) are known compounds, or may be made from knowncompounds, by known methods.

Additional compounds of Formula (A) wherein R² is optionally substitutedaryl or heteroaryl may be prepared from compounds of Formula (AL)wherein X¹ is an atom or group suitable for cross-coupling with an aryl-or heteroaryl-boronic acid in the presence of a suitable palladiumcatalyst and a base under known conditions (see, for example F. Bellina,A. Carpita and R. Rossi, Synthesis 2004, 15, 2419-2440 and A. Suzuki,Journal of Organometallic Chemistry, 2002, 653, 83). Suitable atoms andgroups X¹ include triflates, especially trifluoromethanesulfonyloxy- andhalogens, especially chlorine, bromine and iodine.

In the same way, a compound of Formula (A) wherein R³ is optionallysubstituted aryl or heteroaryl may be prepared from a compound ofFormula (AM) wherein X¹ is as defined previously and a suitable aryl- orheteroaryl boronic acid under palladium catalysed conditions.

Compounds of Formula (AL) and Formula (AM) may be prepared fromCompounds of Formula (AN) and Formula (AO) respectively, by one or moreof the procedures described previously.

Compounds of Formula (AN) and Formula (AO) may be prepared from knowncompounds by known methods.

A compound of Formula (AL) may also be prepared by reacting a compoundof Formula (O) with a compound of Formula (AP) under similar conditionsto those described above for the conversion of a compound of Formula (O)to a compound of Formula (A).

In the same way, a compound of Formula (AM) may be prepared from acompound of Formula (O) and a Compound of Formula (AQ) under identicalconditions.

In a further approach, a compound of formula (A), may be prepared from acompound (Q) by treatment with an aryllead tricarboxylate, in thepresence of a suitable ligand and in a suitable solvent. Similarreactions are described in the literature (for example see, J. Pinhey,B. Rowe, Aust. J. Chem., (1979), 32, 1561-6; J. Morgan, J. Pinhey, J.Chem. Soc. Perkin Trans. 1, (1990), 3, 715-20). Preferably the arylleadtricarboxylate is an aryllead triacetate of formula (AR).

Preferably the ligand is a nitrogen containing heterocycle such asN,N-dimethylamino-pyridine, 1,10-phenanthroline pyridine, bipyridine, orimidazole, and one to ten equivalents of ligand with respect to acompound of formula (J) is preferably used. Most preferably the ligandis N,N-dimethylaminopyridine. The solvent is preferably chloroform,dichloromethane or toluene, most preferably chloroform, or a mixture ofchloroform and toluene. Preferably the reaction is conducted at atemperature of −10° C. to 100° C., most preferably at 40-90° C.).

A compound of formula (AR) may be prepared from a compound of formula(AH) by treatment with lead tetraacetate in a suitable solvent (forexample chloroform) at 25° C. to 10° C. (preferably 25-50° C.), andoptionally in the presence of a catalyst such as mercury diacetate,according to procedures described in the literature (for example see, K.Shimi, G. Boyer, J-P. Finet and J-P. Galy, Letters in Organic Chemistry,(2005), 2, 407-409; J. Morgan and J. Pinhey, J. Chem. Soc. Perkin Trans.1; (1990), 3, 715-720).

In the same way, a compound of formula (AL) may be prepared by treatinga compound of formula (O) with an aryllead triacetate of formula(AS)—itself derived from an arylboronic acid of formula (AT).

A compound of formula (AM) may be similarly prepared from an arylboronicacid of formula (AU) via an aryllead triacetate of formula (AV).

Arylboronic acids of formula (AT), and of formula (AU), are knowncompounds, or may be made by known methods from known compounds.

The compounds of formula I according to the invention can be used asherbicides in unmodified form, as obtained in the synthesis, but theyare generally formulated into herbicidal compositions in a variety ofways using formulation adjuvants, such as carriers, solvents andsurface-active substances. The formulations can be in various physicalforms, for example in the form of dusting powders, gels, wettablepowders, water-dispersible granules, water-dispersible tablets,effervescent compressed tablets, emulsifiable concentrates,microemulsifiable concentrates, oil-in-water emulsions, oil flowables,aqueous dispersions, oily dispersions, suspoemulsions, capsulesuspensions, emulsifiable granules, soluble liquids, water-solubleconcentrates (with water or a water-miscible organic solvent ascarrier), impregnated polymer films or in other forms known, forexample, from the Manual on Development and Use of FAO Specificationsfor Plant Protection Products, 5th Edition, 1999. Such formulations caneither be used directly or are diluted prior to use. Dilutedformulations can be prepared, for example, with water, liquidfertilisers, micronutrients, biological organisms, oil or solvents.

The formulations can be prepared, for example, by mixing the activeingredient with formulation adjuvants in order to obtain compositions inthe form of finely divided solids, granules, solutions, dispersions oremulsions. The active ingredients can also be formulated with otheradjuvants, for example finely divided solids, mineral oils, vegetableoils, modified vegetable oils, organic solvents, water, surface-activesubstances or combinations thereof. The active ingredients can also becontained in very fine microcapsules consisting of a polymer.Microcapsules contain the active ingredients in a porous carrier. Thisenables the active ingredients to be released into their surroundings incontrolled amounts (e.g. slow release). Microcapsules usually have adiameter of from 0.1 to 500 microns. They contain active ingredients inan amount of about from 25 to 95% by weight of the capsule weight. Theactive ingredients can be present in the form of a monolithic solid, inthe form of fine particles in solid or liquid dispersion or in the formof a suitable solution. The encapsulating membranes comprise, forexample, natural and synthetic gums, cellulose, styrene-butadienecopolymers, polyacrylonitrile, polyacrylate, polyester, polyamides,polyureas, polyurethane or chemically modified polymers and starchxanthates or other polymers that are known to the person skilled in theart in this connection. Alternatively it is possible for very finemicrocapsules to be formed wherein the active ingredient is present inthe form of finely divided particles in a solid matrix of a basesubstance, but in that case the microcapsule is not encapsulated.

The formulation adjuvants suitable for the preparation of thecompositions according to the invention are known per se. As liquidcarriers there may be used: water, toluene, xylene, petroleum ether,vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acidanhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone,butylenes carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkylesters of acetic acid, diacetone alcohol, 1,2-dichloropropane,diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycolabietate, diethylene glycol butyl ether, diethylene glycol ethyl ether,diethylene glycol methyl ether, N,N-dimethylformamide, dimethylsulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methylether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone,ethyl acetate, 2-ethyl hexanol, ethylene carbonate,1,1,1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyllactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycolmethyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glyceroldiacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamylacetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene,isopropyl myristate, lactic acid, laurylamine, mesityl oxide,methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyllaurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene,n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleicacid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG 400),propionic acid, propyl lactate, propylene carbonate, propylene glycol,propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate,triethylene glycol, xylenesulfonic acid, paraffin, mineral oil,trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butylacetate, propylene glycol methyl ether, diethylene glycol methyl ether,methanol, ethanol, isopropanol, and higher molecular weight alcohols,such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol,ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone andthe like. Water is generally the carrier of choice for the dilution ofthe concentrates. Suitable solid carriers are, for example, talc,titanium dioxide, pyrophyllite clay, silica, attapulgite clay,kieselguhr, limestone, calcium carbonate, bentonite, calciummontomorillonite, cottonseed husks, wheatmeal, soybean flour, pumice,wood flour, ground walnut shells, lignin and similar materials, asdescribed, for example, in CFR 180.1001. (c) & (d).

A large number of surface-active substances can advantageously be usedboth in solid and in liquid formulations, especially in thoseformulations which can be diluted with a carrier prior to use.Surface-active substances may be anionic, cationic, non-ionic orpolymeric and they may be used as emulsifiying, wetting or suspendingagents or for other purposes. Typical surface-active substances include,for example, salts of alkyl sulfates, such as diethanolammonium laurylsulfate; salts of alkylarylsulfonates, such as calciumdodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products,such as nonylphenol ethoxylate; alcohol-alkylene oxide additionproducts, such as tridecyl alcohol ethoxylate; soaps, such as sodiumstearate; salts of alkylnaphthalenesulfonates, such as sodiumdibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts,such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such assorbitol oleate; quaternary amines, such as lauryl trimethylammoniumchloride, polyethylene glycol esters of fatty acids, such aspolyethylene glycol stearate; block copolymers of ethylene oxide andpropylene oxide; and salts of mono- and di-alkyl phosphate esters; andalso further substances described e.g. in “McCutcheon's Detergents andEmulsifiers Annual”, MC Publishing Corp., Ridgewood, N.J., 1981.

Further adjuvants which can usually be used in pesticidal formulationsinclude crystallisation inhibitors, viscosity-modifying substances,suspending agents, dyes, anti-oxidants, foaming agents, light absorbers,mixing aids, anti-foams, complexing agents, neutralising or pH-modifyingsubstances and buffers, corrosion-inhibitors, fragrances, wettingagents, absorption improvers, micronutrients, plasticisers, glidants,lubricants, dispersants, thickeners, anti-freezes, microbiocides, andalso liquid and solid fertilisers.

The formulations may also comprise additional active substances, forexample further herbicides, herbicide safeners, plant growth regulators,fungicides or insecticides.

The compositions according to the invention can additionally include anadditive comprising an oil of vegetable or animal origin, a mineral oil,alkyl esters of such oils or mixtures of such oils and oil derivatives.The amount of oil additive used in the composition according to theinvention is generally from 0.01 to 10%, based on the spray mixture. Forexample, the oil additive can be added to the spray tank in the desiredconcentration after the spray mixture has been prepared. Preferred oiladditives comprise mineral oils or an oil of vegetable origin, forexample rapeseed oil, olive oil or sunflower oil, emulsified vegetableoil, such as AMIGO® (Rhône-Poulenc Canada Inc.), alkyl esters of oils ofvegetable origin, for example the methyl derivatives, or an oil ofanimal origin, such as fish oil or beef tallow. A preferred additivecontains, for example, as active components essentially 80% by weightalkyl esters of fish oils and 15% by weight methylated rapeseed oil, andalso 5% by weight of customary emulsifiers and pH modifiers. Especiallypreferred oil additives comprise alkyl esters of C₈-C₂₂ fatty acids,especially the methyl derivatives of C₁₂-C₁₈ fatty acids, for examplethe methyl esters of lauric acid, palmitic acid and oleic acid, beingimportant. Those esters are known as methyl laurate (CAS-111-82-0),methyl palmitate (CAS-112-39-0) and methyl oleate (CAS-112-62-9). Apreferred fatty acid methyl ester derivative is Emery® 2230 and 2231(Cognis GmbH). Those and other oil derivatives are also known from theCompendium of Herbicide Adjuvants, 5th Edition, Southern IllinoisUniversity, 2000.

The application and action of the oil additives can be further improvedby combining them with surface-active substances, such as non-ionic,anionic or cationic surfactants. Examples of suitable anionic, non-ionicand cationic surfactants are listed on pages 7 and 8 of WO 97/34485.Preferred surface-active substances are anionic surfactants of thedodecylbenzylsulfonate type, especially the calcium salts thereof, andalso non-ionic surfactants of the fatty alcohol ethoxylate type. Specialpreference is given to ethoxylated C₁₂-C₂₂ fatty alcohols having adegree of ethoxylation of from 5 to 40. Examples of commerciallyavailable surfactants are the Genapol types (Clariant AG). Alsopreferred are silicone surfactants, especially polyalkyl-oxide-modifiedheptamethyltrisiloxanes, which are commercially available e.g. as SilwetL-77®, and also perfluorinated surfactants. The concentration ofsurface-active substances in relation to the total additive is generallyfrom 1 to 30% by weight. Examples of oil additives that consist ofmixtures of oils or mineral oils or derivatives thereof with surfactantsare Edenor ME SU®, Turbocharge® (Syngenta AG, CH) and Actipron® (BP OilUK Limited, GB).

The said surface-active substances may also be used in the formulationsalone, that is to say without oil additives.

Furthermore, the addition of an organic solvent to the oiladditive/surfactant mixture can contribute to a further enhancement ofaction. Suitable solvents are, for example, Solvesso® (ESSO) andAromatic Solvent® (Exxon Corporation). The concentration of suchsolvents can be from 10 to 80% by weight of the total weight. Such oiladditives, which may be in admixture with solvents, are described, forexample, in U.S. Pat. No. 4,834,908. A commercially available oiladditive disclosed therein is known by the name MERGE® (BASFCorporation). A further oil additive that is preferred according to theinvention is SCORE® (Syngenta Crop Protection Canada.)

In addition to the oil additives listed above, in order to enhance theactivity of the compositions according to the invention it is alsopossible for formulations of alkylpyrrolidones, (e.g. Agrimax®) to beadded to the spray mixture. Formulations of synthetic latices, such as,for example, polyacrylamide, polyvinyl compounds or poly-1-p-menthene(e.g. Bond®, Courier® or Emerald®) can also be used. Solutions thatcontain propionic acid, for example Eurogkem Pen-e-trate®, can also bemixed into the spray mixture as activity-enhancing agents.

The herbicidal formulations generally contain from 0.1 to 99% by weight,especially from 0.1 to 95% by weight, of a compound of formula I andfrom 1 to 99.9% by weight of a formulation adjuvant, which preferablyincludes from 0 to 25% by weight of a surface-active substance. Whereascommercial products will preferably be formulated as concentrates, theend user will normally employ dilute formulations.

The rate of application of the compounds of formula I may vary withinwide limits and depends upon the nature of the soil, the method ofapplication (pre- or post-emergence; seed dressing; application to theseed furrow; no tillage application etc.), the crop plant, the weed orgrass to be controlled, the prevailing climatic conditions, and otherfactors governed by the method of application, the time of applicationand the target crop. The compounds of formula I according to theinvention are generally applied at a rate of 1 to 4000 g/ha, especiallyfrom 5 to 1000 g/ha. Preferred formulations have especially thefollowing compositions:

(%=percent by weight):

Emulsifiable concentrates: active ingredient: 1 to 95%, preferably 60 to90% surface-active agent: 1 to 30%, preferably 5 to 20% liquid carrier:1 to 80%, preferably 1 to 35% Dusts: active ingredient: 0.1 to 10%,preferably 0.1 to 5% solid carrier: 99.9 to 90%, preferably 99.9 to 99%Suspension concentrates: active ingredient: 5 to 75%, preferably 10 to50% water: 94 to 24%, preferably 88 to 30% surface-active agent: 1 to40%, preferably 2 to 30% Wettable powders: active ingredient: 0.5 to90%, preferably 1 to 80% surface-active agent: 0.5 to 20%, preferably 1to 15% solid carrier: 5 to 95%, preferably 15 to 90% Granules: activeingredient: 0.1 to 30%, preferably 0.1 to 15% solid carrier: 99.5 to70%, preferably 97 to 85%

The following Examples further illustrate, but do not limit, theinvention.

F1. Emulsifiable concentrates a) b) c) d) active ingredient 5% 10% 25%50% calcium dodecylbenzene- 6%  8%  6%  8% sulfonate castor oilpolyglycol ether 4% —  4%  4% (36 mol of ethylene oxide) octylphenolpolyglycol ether —  4% —  2% (7-8 mol of ethylene oxide) NMP — — 10% 20%arom. hydrocarbon 85%  78% 55% 16% mixture C₉-C₁₂

Emulsions of any desired concentration can be prepared from suchconcentrates by dilution with water.

F2. Solutions a) b) c) d) active ingredient  5% 10% 50% 90%1-methoxy-3-(3-methoxy- — 20% 20% — propoxy)-propane polyethylene glycolMW 400 20% 10% — — NMP — — 30% 10% arom. hydrocarbon 75% 60% — — mixtureC₉-C₁₂

The solutions are suitable for application in the form of microdrops.

F3. Wettable powders a) b) c) d) active ingredient 5% 25%  50%  80% sodium lignosulfonate 4% — 3% — sodium lauryl sulfate 2% 3% — 4% sodiumdiisobutylnaphthalene- — 6% 5% 6% sulfonate octylphenol polyglycol ether— 1% 2% — (7-8 mol of ethylene oxide) highly disperse silicic acid 1% 3%5% 10%  kaolin 88%  62%  35%  —

The active ingredient is thoroughly mixed with the adjuvants and themixture is thoroughly ground in a suitable mill, yielding wettablepowders which can be diluted with water to give suspensions of anydesired concentration.

F4. Coated granules a) b) c) active ingredient 0.1% 5% 15% highlydisperse silicic acid 0.9% 2% 2% inorg. carrier 99.0% 93% 83% (diameter0.1-1 mm) e.g. CaCO₃ or SiO₂

The active ingredient is dissolved in methylene chloride, the solutionis sprayed onto the carrier and the solvent is subsequently evaporatedoff in vacuo.

F5. Coated granules a) b) c) active ingredient 0.1% 5% 15% polyethyleneglycol MW 200 1.0% 2% 3% highly disperse silicic acid 0.9% 1% 2% inorg.carrier 98.0% 92% 80% (diameter 0.1-1 mm) e.g. CaCO₃ or SiO₂

The finely ground active ingredient is applied uniformly, in a mixer, tothe carrier moistened with polyethylene glycol. Non-dusty coatedgranules are obtained in this manner.

F6. Extruder granules a) b) c) d) active ingredient 0.1% 3% 5% 15%sodium lignosulfonate 1.5% 2% 3% 4% carboxymethylcellulose 1.4% 2% 2% 2%kaolin 97.0% 93% 90% 79%

The active ingredient is mixed and ground with the adjuvants and themixture is moistened with water. The resulting mixture is extruded andthen dried in a stream of air.

F7. Dusts a) b) c) active ingredient 0.1% 1% 5% talcum 39.9% 49% 35%kaolin 60.0% 50% 60%

Ready-to-use dusts are obtained by mixing the active ingredient with thecarriers and grinding the mixture in a suitable mill.

F8. Suspension concentrates a) b) c) d) active ingredient   3%  10%  25% 50% ethylene glycol   5%   5%   5%   5% nonylphenol polyglycol ether —  1%   2% — (15 mol of ethylene oxide) sodium lignosulfonate   3%   3%  4%   5% carboxymethylcellulose   1%   1%   1%   1% 37% aqueousformaldehyde 0.2% 0.2% 0.2% 0.2% solution silicone oil emulsion 0.8%0.8% 0.8% 0.8% water  87%  79%  62%  38%

The finely ground active ingredient is intimately mixed with theadjuvants, yielding a suspension concentrate from which suspensions ofany desired concentration can be prepared by dilution with water.

The invention relates also to a method for the selective control ofgrasses and weeds in crops of useful plants, which comprises treatingthe useful plants or the area under cultivation or the locus thereofwith a compound of formula I.

Crops of useful plants in which the compositions according to theinvention can be used include especially cereals, cotton, soybeans,sugar beet, sugar cane, plantation crops, rape, maize and rice, and fornon-selective weed control. The term “crops” is to be understood as alsoincluding crops that have been rendered tolerant to herbicides orclasses of herbicides (for example ALS, GS, EPSPS, PPO, ACCase and HPPDinhibitors) as a result of conventional methods of breeding or geneticengineering. An example of a crop that has been rendered tolerant e.g.to imid-azolinones, such as imazamox, by conventional methods ofbreeding is Clearfield® summer rape (Canola). Examples of crops thathave been rendered tolerant to herbicides by genetic engineering methodsinclude e.g. glyphosate- and glufosinate-resistant maize varietiescommercially available under the trade names RoundupReady® andLibertyLink®. The weeds to be controlled may be both monocotyledonousand dicotyledonous weeds, such as, for example, Stellaria, Nasturtium,Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum,Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus,Sorghum, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus,Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.

Crops are also to be understood as being those which have been renderedresistant to harmful insects by genetic engineering methods, for exampleBt maize (resistant to European corn borer), Bt cotton (resistant tocotton boll weevil) and also Bt potatoes (resistant to Colorado beetle).Examples of Bt maize are the Bt-176 maize hybrids of NK® (SyngentaSeeds). The Bt toxin is a protein that is formed naturally by Bacillusthuringiensis soil bacteria. Examples of toxins and transgenic plantsable to synthesise such toxins are described in EP-A-451 878, EP-A-374753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529. Examplesof transgenic plants that contain one or more genes which code for aninsecticidal resistance and express one or more toxins are KnockOut®(maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton),NewLeaf® (potatoes), NatureGard® and Protexcta®. Plant crops and theirseed material can be resistant to herbicides and at the same time alsoto insect feeding (“stacked” transgenic events). Seed can, for example,have the ability to express an insecticidally active Cry3 protein and atthe same time be glyphosate-tolerant. The term “crops” is to beunderstood as also including crops obtained as a result of conventionalmethods of breeding or genetic engineering which contain so-calledoutput traits (e.g. improved flavour, storage stability, nutritionalcontent).

Areas under cultivation are to be understood as including land where thecrop plants are already growing as well as land intended for thecultivation of those crop plants.

The compounds of formula I according to the invention can also be usedin combination with other herbicides. The following mixtures of thecompound of formula I are especially important.

Preferably, in these mixtures, the compound of the formula I is one ofthose compounds listed in Tables 1 to 81 below:

compound of formula I+acetochlor, compound of formula I+acifluorfen,compound of formula I+acifluorfen-sodium, compound of formulaI+aclonifen, compound of formula I+acrolein, compound of formulaI+alachlor, compound of formula I+alloxydim, compound of formula I+allylalcohol, compound of formula I+ametryn, compound of formulaI+amicarbazone, compound of formula I+amidosulfuron, compound of formulaI+aminopyralid, compound of formula I+amitrole, compound of formulaI+ammonium sulfamate, compound of formula I+anilofos, compound offormula I+asulam, compound of formula I+atrazine, compound of formulaI+azimsulfuron, compound of formula I+BCPC, compound of formulaI+beflubutamid, compound of formula I+benazolin, compound of formulaI+benfluralin, compound of formula I+benfuresate, compound of formulaI+bensulfuron, compound of formula I+bensulfuron-methyl, compound offormula I+bensulide, compound of formula I+bentazone, compound offormula I+benzfendizone, compound of formula I+benzobicyclon, compoundof formula I+benzofenap, compound of formula I+bifenox, compound offormula I+bilanafos, compound of formula I+bispyribac, compound offormula I+bispyribac-sodium, compound of formula I+borax, compound offormula I+bromacil, compound of formula I+bromobutide, compound offormula I+bromoxynil, compound of formula I+butachlor, compound offormula I+butafenacil, compound of formula I+butamifos, compound offormula I+butralin, compound of formula I+butroxydim, compound offormula I+butylate, compound of formula I+cacodylic acid, compound offormula I+calcium chlorate, compound of formula I+cafenstrole, compoundof formula I+carbetamide, compound of formula I+carfentrazone, compoundof formula I+carfentrazone-ethyl, compound of formula I+CDEA, compoundof formula I+CEPC, compound of formula I+chlorflurenol, compound offormula I+chlorflurenol-methyl, compound of formula I+chloridazon,compound of formula I+chlorimuron, compound of formulaI+chlorimuron-ethyl, compound of formula I+chloroacetic acid, compoundof formula I+chlorotoluron, compound of formula I+chlorpropham, compoundof formula I+chlorsulfuron, compound of formula I+chlorthal, compound offormula I+chlorthal-dimethyl, compound of formula I+cinidon-ethyl,compound of formula I+cinmethylin, compound of formula I+cinosulfuron,compound of formula I+cisanilide, compound of formula I+clethodim,compound of formula I+clodinafop, compound of formulaI+clodinafop-propargyl, compound of formula I+clomazone, compound offormula I+clomeprop, compound of formula I+clopyralid, compound offormula I+cloransulam, compound of formula I+cloransulam-methyl,compound of formula I+CMA, compound of formula I+4-CPB, compound offormula I+CPMF, compound of formula I+4-CPP, compound of formula I+CPPC,compound of formula I+cresol, compound of formula I+cumyluron, compoundof formula I+cyanamide, compound of formula I+cyanazine, compound offormula I+cycloate, compound of formula I+cyclosulfamuron, compound offormula I+cycloxydim, compound of formula I+cyhalofop, compound offormula I+cyhalofop-butyl, compound of formula I+2,4-D, compound offormula I+3,4-DA, compound of formula I+daimuron, compound of formulaI+dalapon, compound of formula I+dazomet, compound of formula I+2,4-DB,compound of formula I+3,4-DB, compound of formula I+2,4-DEB, compound offormula I+desmedipham, compound of formula I+dicamba, compound offormula I+dichlobenil, compound of formula I+ortho-dichlorobenzene,compound of formula I+para-dichlorobenzene, compound of formulaI+dichlorprop, compound of formula I+dichlorprop-P, compound of formulaI+diclofop, compound of formula I+diclofop-methyl, compound of formulaI+diclosulam, compound of formula I+difenzoquat, compound of formulaI+difenzoquat metilsulfate, compound of formula I+diflufenican, compoundof formula I+diflufenzopyr, compound of formula I+dimefuron, compound offormula I+dimepiperate, compound of formula I+dimethachlor, compound offormula I+dimethametryn, compound of formula I+dimethenamid, compound offormula I+dimethenamid-P, compound of formula I+dimethipin, compound offormula I+dimethylarsinic acid, compound of formula I+dinitramine,compound of formula I+dinoterb, compound of formula I+diphenamid,compound of formula I+diquat, compound of formula I+diquat dibromide,compound of formula I+dithiopyr, compound of formula I+diuron, compoundof formula I+DNOC, compound of formula I+3,4-DP, compound of formulaI+DSMA, compound of formula I+EBEP, compound of formula I+endothal,compound of formula I+EPTC, compound of formula I+esprocarb, compound offormula I+ethalfluralin, compound of formula I+ethametsulfuron, compoundof formula I+ethametsulfuron-methyl, compound of formula I+ethofumesate,compound of formula I+ethoxyfen, compound of formula I+ethoxysulfuron,compound of formula I+etobenzanid, compound of formula I+fenoxaprop-P,compound of formula I+fenoxaprop-P-ethyl, compound of formulaI+fentrazamide, compound of formula I+ferrous sulfate, compound offormula I+flamprop-M, compound of formula I+flazasulfuron, compound offormula I+florasulam, compound of formula I+fluazifop, compound offormula I+fluazifop-butyl, compound of formula I+fluazifop-P, compoundof formula I+fluazifop-P-butyl, compound of formula I+flucarbazone,compound of formula I+flucarbazone-sodium, compound of formulaI+flucetosulfuron, compound of formula I+fluchloralin, compound offormula I+flufenacet, compound of formula I+flufenpyr, compound offormula I+flufenpyr-ethyl, compound of formula I+flumetsulam, compoundof formula I+flumiclorac, compound of formula I+flumiclorac-pentyl,compound of formula I+flumioxazin, compound of formula I+fluometuron,compound of formula I+fluoroglycofen, compound of formulaI+fluoroglycofen-ethyl, compound of formula I+flupropanate, compound offormula I+flupyrsulfuron, compound of formulaI+flupyrsulfuron-methyl-sodium, compound of formula I+flurenol, compoundof formula I+fluridone, compound of formula I+fluorochloridone, compoundof formula I+fluoroxypyr, compound of formula I+flurtamone, compound offormula I+fluthiacet, compound of formula I+fluthiacet-methyl, compoundof formula I+fomesafen, compound of formula I+foramsulfuron, compound offormula I+fosamine, compound of formula I+glufosinate, compound offormula I+glufosinate-ammonium, compound of formula I+glyphosate,compound of formula I+halosulfuron, compound of formulaI+halosulfuron-methyl, compound of formula I+haloxyfop, compound offormula I+haloxyfop-P, compound of formula I+HC-252, compound of formulaI+hexazinone, compound of formula I+imazamethabenz, compound of formulaI+imazamethabenz-methyl, compound of formula I+imazamox, compound offormula I+imazapic, compound of formula I+imazapyr, compound of formulaI+imazaquin, compound of formula I+imazethapyr, compound of formulaI+imazosulfuron, compound of formula I+indanofan, compound of formulaI+iodomethane, compound of formula I+iodosulfuron, compound of formulaI+iodosulfuron-methyl-sodium, compound of formula I+ioxynil, compound offormula I+isoproturon, compound of formula I+isouron, compound offormula I+isoxaben, compound of formula I+isoxachlortole, compound offormula I+isoxaflutole, compound of formula I+karbutilate, compound offormula I+lactofen, compound of formula I+lenacil, compound of formulaI+linuron, compound of formula I+MAA, compound of formula I+MAMA,compound of formula I+MCPA, compound of formula I+MCPA-thioethyl,compound of formula I+MCPB, compound of formula I+mecoprop, compound offormula I+mecoprop-P, compound of formula I+mefenacet, compound offormula I+mefluidide, compound of formula I+mesosulfuron, compound offormula I+mesosulfuron-methyl, compound of formula I+mesotrione,compound of formula I+metam, compound of formula I+metamifop, compoundof formula I+metamitron, compound of formula I+metazachlor, compound offormula I+methabenzthiazuron, compound of formula I+methylarsonic acid,compound of formula I+methyldymron, compound of formula I+methylisothiocyanate, compound of formula I+metobenzuron, compound of formulaI+metolachlor, compound of formula I+S-metolachlor, compound of formulaI+metosulam, compound of formula I+metoxuron, compound of formulaI+metribuzin, compound of formula I+metsulfuron, compound of formulaI+metsulfuron-methyl, compound of formula I+MK-616, compound of formulaI+molinate, compound of formula I+monolinuron, compound of formulaI+MSMA, compound of formula I+naproanilide, compound of formulaI+napropamide, compound of formula I+naptalam, compound of formulaI+neburon, compound of formula I+nicosulfuron, compound of formulaI+nonanoic acid, compound of formula I+norflurazon, compound of formulaI+oleic acid (fatty acids), compound of formula I+orbencarb, compound offormula I+orthosulfamuron, compound of formula I+oryzalin, compound offormula I+oxadiargyl, compound of formula I+oxadiazon, compound offormula I+oxasulfuron, compound of formula I+oxaziclomefone, compound offormula I+oxyfluorfen, compound of formula I+paraquat, compound offormula I+paraquat dichloride, compound of formula I+pebulate, compoundof formula I+pendimethalin, compound of formula I+penoxsulam, compoundof formula I+pentachlorophenol, compound of formula I+pentanochlor,compound of formula I+pentoxazone, compound of formula I+pethoxamid,compound of formula I+petrolium oils, compound of formulaI+phenmedipham, compound of formula I+phenmedipham-ethyl, compound offormula I+picloram, compound of formula I+picolinafen, compound offormula I+pinoxaden, compound of formula I+piperophos, compound offormula I+potassium arsenite, compound of formula I+potassium azide,compound of formula I+pretilachlor, compound of formula I+primisulfuron,compound of formula I+primisulfuron-methyl, compound of formulaI+prodiamine, compound of formula I+profluazol, compound of formulaI+profoxydim, compound of formula I+prometon, compound of formulaI+prometryn, compound of formula I+propachlor, compound of formulaI+propanil, compound of formula I+propaquizafop, compound of formulaI+propazine, compound of formula I+propham, compound of formulaI+propisochlor, compound of formula I+propoxycarbazone, compound offormula I+propoxycarbazone-sodium, compound of formula I+propyzamide,compound of formula I+prosulfocarb, compound of formula I+prosulfuron,compound of formula I+pyraclonil, compound of formula I+pyraflufen,compound of formula I+pyraflufen-ethyl, compound of formulaI+pyrazolynate, compound of formula I+pyrazosulfuron, compound offormula I+pyrazosulfuron-ethyl, compound of formula I+pyrazoxyfen,compound of formula I+pyribenzoxim, compound of formula I+pyributicarb,compound of formula I+pyridafol, compound of formula I+pyridate,compound of formula I+pyriftalid, compound of formula I+pyriminobac,compound of formula I+pyriminobac-methyl, compound of formulaI+pyrimisulfan, compound of formula I+pyrithiobac, compound of formulaI+pyrithiobac-sodium, compound of formula I+quinclorac, compound offormula I+quinmerac, compound of formula I+quinoclamine, compound offormula I+quizalofop, compound of formula I+quizalofop-P, compound offormula I+rimsulfuron, compound of formula I+sethoxydim, compound offormula I+siduron, compound of formula I+simazine, compound of formulaI+simetryn, compound of formula I+SMA, compound of formula I+sodiumarsenite, compound of formula I+sodium azide, compound of formulaI+sodium chlorate, compound of formula I+sulcotrione, compound offormula I+sulfentrazone, compound of formula I+sulfometuron, compound offormula I+sulfometuron-methyl, compound of formula I+sulfosate, compoundof formula I+sulfosulfuron, compound of formula I+sulfuric acid,compound of formula I+tar oils, compound of formula I+2,3,6-TBA,compound of formula I+TCA, compound of formula I+TCA-sodium, compound offormula I+tebuthiuron, compound of formula I+tepraloxydim, compound offormula I+terbacil, compound of formula I+terbumeton, compound offormula I+terbuthylazine, compound of formula I+terbutryn, compound offormula I+thenylchlor, compound of formula I+thiazopyr, compound offormula I+thifensulfuron, compound of formula I+thifensulfuron-methyl,compound of formula I+thiobencarb, compound of formula I+tiocarbazil,compound of formula I+topramezone, compound of formula I+tralkoxydim,compound of formula I+tri-allate, compound of formula I+triasulfuron,compound of formula I+triaziflam, compound of formula I+tribenuron,compound of formula I+tribenuron-methyl, compound of formula I+tricamba,compound of formula I+triclopyr, compound of formula I+trietazine,compound of formula I+trifloxysulfuron, compound of formulaI+trifloxysulfuron-sodium, compound of formula I+trifluralin, compoundof formula I+triflusulfuron, compound of formulaI+triflusulfuron-methyl, compound of formula I+trihydroxytriazine,compound of formula I+tritosulfuron, compound of formulaI+[3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]aceticacid ethyl ester (CAS RN 353292-31-6), compound of formulaI+4-[(4,5-dihydro-3-methoxy-4-methyl-5-oxo)-1H-1,2,4-triazol-1-ylcarbonylsulfamoyl]-5-methylthiophene-3-carboxylicacid (BAY636), compound of formula I+BAY747 (CAS RN 335104-84-2),compound of formula I+topramezone (CAS RN 210631-68-8), compound offormulaI+4-hydroxy-3-[[2-[(2-methoxyethoxy)methyl]-6-(trifluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.]oct-3-en-2-one(CAS RN 352010-68-5), and compound of formulaI+4-hydroxy-3-[[2-(3-methoxypropyl)-6-(difluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3-en-2-one.

The mixing partners of the compound of formula I may also be in the formof esters or salts, as mentioned e.g. in The Pesticide Manual, TwelfthEdition, British Crop Protection Council, 2000.

The mixing ratio of the compound of formula I to the mixing partner ispreferably from 1:100 to 1000:1.

The mixtures can advantageously be used in the above-mentionedformulations (in which case “active ingredient” relates to therespective mixture of compound of formula I with the mixing partner).

The compounds of formula I according to the invention can also be usedin combination with safeners. Preferably, in these mixtures, thecompound of the formula I is one of those compounds listed in Tables 1to 81 below. The following mixtures with safeners, especially, come intoconsideration:

compound of formula I+cloquintocet-mexyl, compound of formulaI+cloquintocet acid and salts thereof, compound of formulaI+fenchlorazole-ethyl, compound of formula I+fenchlorazole acid andsalts thereof, compound of formula I+mefenpyr-diethyl, compound offormula I+mefenpyr diacid, compound of formula I+isoxadifen-ethyl,compound of formula I+isoxadifen acid, compound of formula I+furilazole,compound of formula I+furilazole R isomer, compound of formulaI+benoxacor, compound of formula I+dichlormid, compound of formulaI+AD-67, compound of formula I+oxabetrinil, compound of formulaI+cyometrinil, compound of formula I+cyometrinil Z-isomer, compound offormula I+fenclorim, compound of formula I+cyprosulfamide, compound offormula I+naphthalic anhydride, compound of formula I+flurazole,compound of formula I+CL 304,415, compound of formula I+dicyclonon,compound of formula I+fluxofenim, compound of formula I+DKA-24, compoundof formula I+R-29148 and compound of formula I+PPG-1292. A safeningeffect can also be observed for the mixtures compound of the formulaI+dymron, compound of the formula I+MCPA, compound of the formulaI+mecopropand compound of the formula I+mecoprop-P.

The above-mentioned safeners and herbicides are described, for example,in the Pesticide Manual, Twelfth Edition, British Crop ProtectionCouncil, 2000. R-29148 is described, for example by P. B. Goldsbrough etal., Plant Physiology, (2002), Vol. 130 pp. 1497-1505 and referencestherein and PPG-1292 is known from WO09211761.

The rate of application of safener relative to the herbicide is largelydependent upon the mode of application. In the case of field treatment,generally from 0.001 to 5.0 kg of safener/ha, preferably from 0.001 to0.5 kg of safener/ha, and generally from 0.001 to 2 kg of herbicide/ha,but preferably from 0.005 to 1 kg/ha, are applied.

The mixtures can advantageously be used in the above-mentionedformulations (in which case “active ingredient” relates to therespective mixture of compound of formula I with the mixing partner).

The following Examples illustrate the invention further but do not limitthe invention.

PREPARATION EXAMPLES Example 1 Preparation of2-(2,4,6-trimethylphenyl)-5-(tetrahydrofuran-3-ylmethyl)cyclohexane-1,3-dione

Step 1 Preparation of(3,5-dimethoxyphenyl)(tetrahydrofuran-3-yl)methanol

Magnesium turnings (8.5 g, 0.35 mol) are activated by stirring at roomtemperature overnight under argon and suspended in anhydroustetrahydrofuran (60 ml). 10 ml of a solution of3,5-dimethoxychlorobenzene (60.4 g, 0.35 mol) in anhydroustetrahydrofuran (75 mL) is added, followed by a crystal of iodine, andthe mixture is placed in an ultrasonic bath for 10 minutes. A further 10mL of the solution of 3,5-dimethoxychlorobenzene in tetrahydrofuran isadded and reaction is heated at 80° C. for 1 h. The remainder of thestarting material is added dropwise to the reaction mixture at 80° C.over 50 minutes, then heating is continued at 80° C. for a further 30minutes. The reaction mixture is cooled to below room temperature in anice/water bath and a solution of tetrahydrofuran-3-carbaldehyde (35 g,0.35 mol) in anhydrous tetrahydrofuran (35 mL) is added dropwise over 30minutes. Once the addition is complete, the reaction mixture is stirredat room temperature overnight. The reaction mixture is decanted and 2Maqueous hydrochloric acid is carefully added to the decanted solution,until the pH of the reaction mixture reaches pH 1. The reaction mixtureis extracted with ethyl acetate (4×100 mL) and the organic extracts arecombined, washed with brine, dried over anhydrous magnesium sulfate,filtered and the filtrate concentrated in vacuo. The residue is purifiedby column chromatography on silica gel to give(3,5-dimethoxyphenyl)(tetrahydrofuran-3-yl)methanol as a yellow oil.

¹H NMR (CDCl₃, ppm) δ 6.51 (dd, 2H), 6.39 (q, 1H), 4.46 (dd, 1H),3.98-3.84 (m, 2H), 3.80 (s, 3H), 3.79 (s, 3H), 3.77-3.47 (m, 2H),2.65-2.55 (m, 1H), 2.12-1.96 (m, 2H)

Step 2 Preparation of5-(tetrahydrofuran-3-ylmethyl)cyclohexane-1,3-dione

Liquid ammonia (˜300 mL) is added to a cold (−78° C.) 500 mLthree-necked round bottomed flask fitted with a cold finger, under ablanket of nitrogen. A solution of(3,5-dimethoxyphenyl)(tetrahydrofuran-3-yl)methanol (10.0 g, 42 mmol) inethanol (10 mL) is added. Lithium wire is added in ˜100 mg pieces untila blue colour persists for several minutes. When the blue colour fades,more ethanol (5 mL) is added, together with further portions of lithiumwire (˜100 mg portions) and this process is repeated until the reactionis judged to be complete (conveniently by mass spectrometric analysis).The reaction mixture is allowed to warm to room temperature, and oncethe ammonia is evaporated, a saturated solution of aqueous ammoniumchloride (150 mL) is added, followed by ethyl acetate (150 mL) and themixture is stirred until the off-white solid dissolves. The reactionmixture is poured into a separating funnel, the layers are separated andthe aqueous layer is extracted with ethyl acetate. The organic extractsare combined, dried over anhydrous magnesium sulfate, filtered and thefiltrate concentrated in vacuo.

The residue is stirred overnight at room temperature in a mixture oftetrahydrofuran (100 ml) and 2M aqueous hydrochloric acid (100 mL), thenextracted into ethyl acetate. The organic extracts are washed withbrine, dried over anhydrous magnesium sulfate, filtered and the filtrateconcentrated in vacuo to give5-(tetrahydrofuran-3-ylmethyl)cyclohexane-1,3-dione as an off-whitesolid, used without further purification in the next step.

Step 3 Preparation of2-(2,4,6-trimethylphenyl)-5-(tetrahydrofuran-3-ylmethyl)cyclohexane-1,3-dione

Step 3a

Iodobenzene diacetate (11.5 g, 35.6 mmol) and sodium carbonate (3.8 g,35.6 mmol) are suspended in water (70 mL) and stirred at roomtemperature for 30 minutes. Meanwhile, a solution of sodium carbonate(3.8 g, 35.6 mmol) in water (70 mL) is added to5-(tetrahydro-furan-3-ylmethyl)cyclohexane-1,3-dione (7.0 g, 35.6 mmol)and this mixture is stirred for 20 minutes to produce a sparinglysoluble orange suspension. The two reaction mixtures are then combinedand the mixture stirred at room temperature for 3 hours. The solidprecipitate is removed by filtration, and the filtrate is extracted withdichloromethane. The organic extracts are dried over anhydrous magnesiumsulfate, filtered and the filtrate concentrated in vacuo to give ayellow oil. The oil is triturated with ether and filtered to give thedesired iodonium ylide as a yellow solid.

¹H NMR (CDCl₃, ppm) δ 7.84 (dd, 2H), 7.53 (m, 1H), 7.36 (t, 2H), 3.89(t, 1H), 3.83 (m, 1H), 3.73 (q, 1H), 3.29 (t, 1H), 2.76-2.71 (m, 2H),2.37-2.24 (m, 3H), 2.12-2.00 (m, 2H), 1.51-1.42 (m, 3H).

Step 3b

The iodonium ylide (1.5 g, 3.77 mmol) prepared in Step 3a is suspendedin a mixture of 1,2-dimethoxyethane (40 ml) and water (10 mL).2,4,6-Trimethylphenylboronic acid (0.54 g, 4.14 mmol) is added, followedby lithium hydroxide monohydrate (0.48 g, 11.3 mmol), tetrabutylammoniumbromide (1.25 g, 3.77 mmol) and palladium (II) acetate (0.042 g, 0.21mmol) and the mixture is heated at 50-52° C. for 6 h 30 and then allowedto cool to room temperature. The reaction mixture is acidified with 2Naqueous hydrochloric acid, and then extracted into ethyl acetate. Theorganic extracts are combined and partitioned with 0.5M aqueouspotassium carbonate solution. The organic phase is discarded. Theaqueous phase is acidified to pH 1 with concentrated hydrochloric acidand extracted with ethyl acetate. The organic extracts are combined,dried over anhydrous magnesium sulfate, filtered and the filtrateconcentrated in vacuo. The residue is purified by column chromatographyon silica gel to give2-(2,4,6-trimethylphenyl)-5-(tetrahydrofuran-3-ylmethyl)cyclohexane-1,3-dioneas a pale yellow solid, m.p. 62-64° C.

¹H NMR (CDCl₃, ppm) δ 6.94 (s, 2H), 5.50 (br s, 1H), 3.96 (br t, 1H),3.89 (m, 1H), 3.78 (q, 1H), 3.36 (t, 1H), 2.71-2.66 (br m, 2H),2.44-2.22 (m, 7H), 2.09-2.03 (m, 7H), 1.60-1.50 (br m, 3H).

Example 2 Preparation of2-(2,6-diethyl-4-methylphenyl)-5-(tetrahydropyran-4-ylmethyl)cyclohexane-1,3-dione

Step 1 Preparation of 4-(methoxymethylene)tetrahydropyran

Methoxymethyltriphenylphosphonium chloride (81.8 g) is suspended in dryTHF (200 ml) and stirred under nitrogen at 0° C. A 1 molar solution oflithium bis(trimethylsilyl)amide in THF (239 ml) is transferred to adropping funnel by cannular under nitrogen and added over 20 minutes.

The resulting red-brown solution is stirred at 0-20° C. for 1 hour. Themixture is then cooled to −25° C. and tetrahydro-4H-pyran-4-one (20 ml)is added over 10 minutes. The cooling bath is removed and the mixture isallowed to reach room temperature, then stirred for 22 hours. Thereaction mixture is poured into water (400 ml) and extracted into ether(2×400 ml). The organic extracts are combined, washed with water (2×400ml) and brine (400 ml), dried over anhydrous magnesium sulfate, filteredand the filtrate is concentrated in vacuo. The residue is treated with800 ml ether:hexane (1:1), stirred for 15 mins, then cooled in an icebath for 10 mins and filtered under vacuum to remove the precipitatedtriphenylphosphine oxide. The filtrate is concentrated, treated againwith 400 ml ether:hexane (1:1), stirred for 15 minutes, then cooled inan ice bath and additional precipitate removed by filtration. Thefiltrate is concentrated giving 25.371 g of a brown oil, which isfurther purified by vacuum distillation to afford4-(methoxymethylene)-tetrahydropyran (b.p. 66° C./20 mmHg)

¹H NMR (CDCl₃, ppm) δ 5.82 (s, 1H), 3.61 (m, 4H), 3.53 (s, 3H), 2.28 (t,2H), 2.04 (t, 2H)

Step 2 Preparation of tetrahydropyran-4-carboxaldehyde

A mixture of 4-(methoxymethylene)tetrahydropyran (17.18 g, 134 mmol) andtoluene-4-sulphonic acid hydrate (35.76 g, 188 mmol) in a mixture ofwater (90 ml) and THF (90 ml) is stirred at room temperature for 4½hours. The mixture is treated with a saturated aqueous solution ofNaHCO₃ (300 ml) and stirred until effervescence ceased. The mixture istransferred to a separating funnel, brine (100 ml) is added, and themixture is partitioned with dichloromethane (4×150 ml). The organicextracts are combined, dried over anhydrous magnesium sulfate, filteredand the filtrate concentrated in vacuo to affordtetrahydropyran-4-carboxaldehyde.

¹H NMR (CDCl₃, ppm) δ_(H) 9.61 (s, 1H), 3.92 (m, 2H), 3.45 (m, 2H),2.50-2.43 (m, 1H), 1.85-1.79 (m, 2H), 1.70-1.61 (m, 2H).

Step 3 Preparation of (3,5-dimethoxyphenyl)(tetrahydropyran-4-yl)methanol

A solution of tetrahydropyran-4-carboxaldehyde (16.0 g, 0.14 mol) intetrahydrofuran (60 ml) is added dropwise over 1 hour to a 1 M solutionof 3,5-dimethoxyphenylmagnesium chloride in tetrahydrofuran (140 ml),maintaining the reaction at or below reflux by external cooling. Oncethe addition is complete, and the exotherm has subsided, the reactionmixture is allowed to stir at room temperature overnight. A solution ofdilute aqueous hydrochloric acid (300 ml) is added carefully and thereaction mixture is extracted with ethyl acetate. The organic extract isdried over anhydrous magnesium sulfate, filtered, and the filtrateevaporated in vacuo. Purification by column chromatography on silica gelgives (3,5-dimethoxyphenyl) (tetrahydropyran-4-yl)methanol as a creamsolid.

¹H NMR (CDCl₃, ppm) δ 6.47 (d, 2H), 6.38 (t, 1H), 4.29 (d, 1H), 4.01(dd, 1H), 3.90 (dd, 1H), 3.36 (m, 1H), 3.29 (m, 1H), 1.96 (br s, 1H),1.92-1.87 (m, 1H), 1.83-1.77 (m, 1H), 1.51-1.18 (m, 3H).

Step 4 Preparation of5-(tetrahydropyran-4-ylmethyl)cyclohexane-1,3-dione

Ammonia (pre-dried using sodium and iron (III) chloride) (approx 200 mL)is allowed to distil into a flask containing (3,5-dimethoxyphenyl)(tetrahydropyran-4-yl)methanol (308 mg, 1.3 mmol) in ethanol (2 mL), andlithium wire is added portionwise to the reaction mixture until thereaction mixture retains a blue colour. A further quantity of ethanol(˜2 mL) is then added, followed by the addition of a further smallquantity of lithium, and the reaction mixture stirred until the bluecolour persists for a few minutes. The ammonia is evaporated, and theresultant white solution is taken up into saturated aqueous ammoniumchloride solution, and extracted with ethyl acetate. The organicextracts are washed with brine, dried over anhydrous magnesium sulfate,filtered and the filtrate concentrated in vacuo.

The residue is dissolved in a 1:1 mixture of tetrahydrofuran and diluteaqueous hydrochloric acid (50 mL) and the reaction mixture is stirred atroom temperature overnight. The reaction is extracted into ethyl acetateand the organic extracts are combined, washed with brine, dried overanhydrous magnesium sulfate, filtered and the filtrate is concentratedin vacuo to give a white solid. Recrystallisation from ethylacetate/hexane gives 5-(tetrahydropyran-4-ylmethyl)cyclohexane-1,3-dioneas a white solid, m.p. 129-130° C.

Step 5 Preparation of

Step 5a

Iodobenzene diacetate (184 mg, 0.57 mmol) and sodium carbonate (60 mg,0.57 mmol) are suspended in water (20 mL) and the mixture is stirred atroom temperature for 30 minutes to give a pale yellow suspension.Meanwhile, a solution of sodium carbonate (60 mg, 0.57 mmol) in water(10 mL) and ethanol (10 mL) is added to5-(tetrahydropyran-4-ylmethyl)cyclohexane-1,3-dione (120 mg, 0.57 mmol)and the reaction is stirred at room temperature for 20 minutes. The twomixtures are then combined and the reaction mixture is stirred at roomtemperature for 1 hour. The reaction mixture is then partitioned betweenbrine and dichloromethane, and the organic extracts are combined, driedover anhydrous magnesium sulfate, filtered and the filtrate evaporatedin vacuo to give the desired iodonium ylide, used without furtherpurification in the next step.

¹H NMR (CDCl₃, ppm) δ_(H) 7.79-7.76 (m, 2H), 7.46 (m, 1H), 7.33-7.24 (m,2H), 3.86 (dd, 2H), 3.28 (m, 2H), 2.63 (dd, 2H), 2.26-2.11 (m, 3H),1.56-1.47 (m, 3H), 1.23 (t, 2H), 1.21-1.11 (m, 2H).

Step 5b

The iodonium ylide (193 mg, 0.47 mmol) prepared in Step 5a is added to amixture of 2,6-diethyl-4-methylphenylboronic acid (90 mg, 0.47 mmol),tetrabutylammonium bromide (151 mg, 0.47 mmol), lithium hydroxidemonohydrate (60 mg, 1.4 mmol) and palladium (II) acetate (catalyticamount) in aqueous 1,2-dimethoxyethane and the reaction mixture isheated at 50° C. for 3 hours. The reaction is then cooled, diluteaqueous hydrochloric acid is added, and the mixture is extracted withethyl acetate. The organic extracts are combined, dried over anhydrousmagnesium sulfate, filtered and the filtrate is concentrated in vacuo.The residue is purified by column chromatography on silica gel to give2-(2,6-diethyl-4-methylphenyl)-5-(tetrahydropyran-4-ylmethyl)cyclohexane-1,3-dione

¹H NMR (CDCl₃, ppm) δ 7.0 (s, 2H), 5.50 (br s, 1H), 3.98 (br dd, 2H),3.40 (br t, 2H), 2.68-2.63 (m, 2H), 2.45-2.25 (m, 10H), 1.69-1.55 (m,3H), 1.44 (br t, 2H), 1.35-1.20 (m, 2H), 1.08 (q, 6H).

Example 3 Preparation of2-(2,6-diethyl-4-methylphenyl)-5-([1,3]dioxolan-2-ylmethyl)cyclohexane-1,3-dione(Compound A-6)

Step 1 Preparation of2-(3,5-dimethoxy-cyclohexa-2,5-dienylmethyl)-[1,3]-dioxolane

Ammonia (pre-dried using sodium and iron (III) chloride) (approx 60 mL)is allowed to distil into a flask containing2-(3,5-dimethoxybenzyl)-[1,3]-dioxolane (1.0 g, 4.46 mmol) in ethanol (3mL), and lithium wire is added portionwise to the reaction mixture untilthe reaction mixture retains a blue colour for ten minutes. Ethanol (1mL) is then added, and the mixture stirred for 20-25 minutes at −33° C.The ammonia is evaporated, and the resultant mixture is taken up intosaturated aqueous ammonium chloride solution (20 ml), and extracted withethyl acetate (3×25 ml). The organic extracts are washed with brine,dried over anhydrous magnesium sulfate, filtered and the filtrateconcentrated in vacuo to give2-(3,5-dimethoxy-cyclohexa-2,5-dienylmethyl)-[1,3]-dioxolane.

¹H NMR (CDCl₃, ppm) δ 5.00 (t, 1H), 4.70 (m, 2H), 4.01 and 3.89 (2×m,4H), 3.58 (s, 6H), 3.20 (m, 1H), 2.79 (m, 2H), 1.79 (m, 2H)

Step 2 Preparation of5-([1,3]-dioxolan-2-ylmethyl)-cyclohexane-1,3-dione

A solution of2-(3,5-dimethoxycyclohexa-2,5-dienylmethyl)-[1,3]-dioxolane (730 mgs,3.2 mmol) in a mixture of 10% aqueous hydrochloric acid (2.9 ml) andtetrahydrofuran (29 ml) is stirred at room temperature for ¾ hour. Thereaction mixture is poured into an aqueous solution of saturatedpotassium carbonate and extracted with ethyl acetate. The organicextract is discarded. The aqueous extract is acidified with diluteaqueous hydrochloric acid and extracted with ethyl acetate. The organicextract is dried over anhydrous magnesium sulfate, filtered and thenfiltrate evaporated in vacuo to give5-([1,3]-dioxolan-2-ylmethyl)-cyclohexane-1,3-dione as a white solid,used without further purification in the next step.

Step 3 Preparation of2-(2,6-diethyl-4-methylphenyl)-5-([1,3]dioxolan-2-ylmethyl)cyclohexane-1,3-dione

Step 3a

Iodobenzene diacetate (454 mg, 1.4 mmol) and sodium carbonate (148 mg,1.4 mmol) are suspended in water (6.5 mL) and the mixture is stirred atroom temperature for 30 minutes. Meanwhile, a solution of sodiumcarbonate (148 mg, 1.4 mmol) in water (6.5 ml) and is added to5-([1,3]-dioxolan-2-ylmethyl)cyclohexane-1,3-dione (280 mgs, 1.4 mmol)and this mixture is stirred at room temperature for 20 minutes. The twomixtures are then combined and the reaction mixture is stirred at roomtemperature for 2 hours. The reaction mixture is extracted withdichloromethane, and the organic extracts are combined, washed withbrine, dried over anhydrous magnesium sulfate, filtered and the filtrateevaporated in vacuo to give the desired iodonium ylide, used withoutfurther purification in the next step.

Step 3b

The iodonium ylide (477 mg, 1.19 mmol) prepared in Step 3a is added to amixture of 2,6-diethyl-4-methylphenylboronic acid (343 mg, 1.79 mmol),tetrabutylammonium bromide (385 mg, 1.19 mmol), lithium hydroxidemonohydrate (151 mg, 3.57 mmol) and palladium (II) acetate (13 mgs) in amixture of 1,2-dimethoxyethane (10.8 ml) and water (2.7 ml) and thereaction mixture is heated at 55° C. for 5 hours. The reaction is thencooled, dilute aqueous hydrochloric acid is added, and the mixture isextracted with ethyl acetate. The organic extracts are combined, washedwith water, dried over anhydrous magnesium sulfate, filtered and thefiltrate is concentrated in vacuo. The residue is purified by columnchromatography on silica gel to give2-(2,6-diethyl-4-methylphenyl)-5-([1,3]dioxolan-2-ylmethyl)cyclohexane-1,3-dione

¹H NMR (CDCl₃, ppm) δ_(H) 6.98 (br s, 2H), 4.98 (t, 1H), 4.01-3.88 (2×m,4H), 2.75 (m, 2H), 2.60-2.25 (m, 10H), 1.85 (m, 2H), 1.05 (m, 6H)

Example 4 Preparation of2-(4′-Chloro-4-methylbiphenyl-3-yl)-5-[1,3]dioxolan-2-ylmethylcyclohexane-1,3-dione

Step 1 Preparation of2-(4′-Chloro-4-methylbiphenyl-3-yl)-5-[1,3]dioxolan-2-ylmethylcyclohexane-1,3-dione

To a solution of 5-[1,3]dioxolan-2-ylmethylcyclohexane-1,3-dione (1.43g, 7.22 mmol) in a mixed solvent system of chloroform (72 ml) andtoluene (18 ml) is added N,N-dimethylaminopyridine (4.40 g, 36.08 mmol)and the solution is stirred at room temperature for 10 minutes. To thismixture is then added 4′-chloro-4-methylbiphenyl-3-yllead triacetate(described in WO 2008/071405) (4.95 g, 7.91 mmol) in one portion,followed by heating at 80° C. for 2 hours. After cooling to roomtemperature the solution is diluted with dichloromethane (90 ml) andquenched with 1M hydrochloric acid (90 ml). The resulting precipitate isfiltered through celite and the residue washed with additionaldichloromethane (20 ml). The biphasic solution is separated and theorganic layer further washed with 1M hydrochloric acid (45 ml). Organicsare finally passed through a phase separator then concentrated in vacuoto afford the crude product as a yellow oil. After flash columnchromatography on silica (7:1 ethyl acetate/hexane eluant)2-(4′-chloro-4-methylbiphenyl-3-yl)-5-[1,3]dioxolan-2-ylmethylcyclohexane-1,3-dioneis afforded as a cream solid.

Example 5 Preparation of2-(4′-Chloro-4-methylbiphenyl-3-yl)-5-[1,3]dioxan-2-ylmethylcyclohexane-1,3-dione

Step 1 Preparation of[4-(4′-Chloro-4-methylbiphenyl-3-yl)-3,5-dioxocyclohexyl]-acetaldehyde

To a solution of2-(4′-chloro-4-methylbiphenyl-3-yl)-5-[1,3]dioxolan-2-ylmethylcyclohexane-1,3-dione(0.275 g, 0.69 mmol) in tetrahydrofuran (5 ml) is added 6M hydrochloricacid (2 ml), and the reaction mixture is stirred at room temperature for1.5 hours. Additional 6M hydrochloric acid (1 ml) is added and thesolution is heated at 50° C. for an additional 2 hours. After cooling toroom temperature the reaction mixture is concentrated and the residuepartitioned between distilled water (20 ml) and dichloromethane (20 ml).After extraction of the aqueous phase with dichloromethane (3×10 ml) allorganic fractions are combined then passed through a phase separator.The fitrate is concentrated in vacuo to afford[4-(4′-Chloro-4-methylbiphenyl-3-yl)-3,5-dioxocyclohexyl]-acetaldehydeas a white foam.

¹H NMR (CDCl₃): δ9.84 (m, 1H), 7.49 (m, 3H), 7.38 (m 3H), 7.24 (m 1H),5.60-5.65 (m, 1H), 2.33-2.90 (m, 5H), 1.88 (m, 1H), 1.71 (m, 1H), 1.27(s, 3H).

Step 2 Preparation of2-(4′-Chloro-4-methylbiphenyl-3-yl)-5-[1,3]dioxan-2-ylmethylcyclohexane-1,3-dione

To a solution of[4-(4′-chloro-4-methylbiphenyl-3-yl)-3,5-dioxocyclohexyl]-acetaldehyde(0.080 g, 0.23 mmol) and propane-1,3-diol (0.021 g, 0.27 mmol) inanhydrous toluene (4 ml) is added a single crystal ofpara-toluenesulfonic acid and the mixture is stirred at 80° C. for 45minutes. After cooling to room temperature the solution is concentratedin vacuo to afford a crude product which is purified by flash columnchromatography on silica (ethyl acetate eluant) to afford2-(4′-chloro-4-methylbiphenyl-3-yl)-5-[1,3]dioxan-2-ylmethylcyclohexane-1,3-dioneas a white foam.

Compounds in Table 100 below were prepared by similar methods usingappropriate starting materials.

TABLE 100 Compound ¹H NMR (CDCl₃ unless stated), or other NumberStructure physical data A-1 

δ_(H) 6.94 (s, 2H), 5.50 (br s, 1H), 3.96 (br t, 1H), 3.89 (m, 1H), 3.78(q, 1H), 3.36 (t, 1H), 2.71-2.66 (br m, 2H), 2.44-2.22 (m, 7H),2.09-2.03 (m, 7H), 1.60-1.50 (br m, 3H). A-2 

δ_(H) 7.50-7.45 (m, 3H), 7.40-7.38 (m, 3H), 7.26-7.24 (m, 1H), 3.97 (brt, 1H), 3.90 (m, 1H), 3.78 (q, 1H), 3.37 (td, 1H), 2.70 (br d, 2H),2.39-2.26 (m, 4H), 2.18- 2.10 (m, 4H), 1.60-1.53 (br m, 3H). A-3 

δ_(H) 6.98 (2H, s), 3.95 (t, 1H), 3.91-3.86 (br m, 1H), 3.77 (q, 1H),3.36 (t, 1H), 2.68 (br d, 2H), 2.39-2.29 (m, 11H), 2.15-2.04 (m, 1H),1.60-1.52 (br m, 3H), 1.07 (q, 6H). A-4 

δ_(H) 7.53-7.46 (m, 3H), 7.40-7.36 (m, 3H), 7.21 (dd, 1H), 5.14 (br s,1H), 3.93 (m, 1H), 3.89-3.84 (br m, 1H), 3.75 (q, 1H), 3.34 (m, 1H),2.67 (br d, 2H), 2.49- 2.39 (m, 2H), 2.36-2.23 (br m, 4H), 2.14- 2.05(m, 1H), 1.57-1.49 (m, 3H), 1.16- 1.10 (m, 3H). A-5 

δ_(H) 7.0 (s, 2H), 5.50 (br s, 1H), 3.98 (br dd, 2H), 3.40 (br t, 2H),2.68-2.63 (m, 2H), 2.45-2.25 (m, 10H), 1.69-1.55 (m, 3H), 1.44 (br t,2H), 1.35-1.20 (m, 2H), 1.08 (q, 6H). A-6 

δ_(H) 6.98 (br s, 2H), 4.98 (t, 1H), 4.01-3.88 (2 X m, 4H), 2.75 (m,2H), 2.60-2.25 (m, 10H), 1.85 (m, 2H), 1.05 (m, 6H). A-7 

δ_(H) 6.98 (br s, 2H), 5.42 (s, 1H), 4.68 (t, 1H), 4.14 (m, 2H), 3.78(m, 2H), 2.20-2.75 (m, 9H), 2.32 (s, 3H), 2.10(m, 1H), 1.78 (m, 2H), 1.3(m, 1H), 1.08 (m, 6H). A-8 

δ_(H) 6.98 (br s, 2H), 5.42 (s, 1H), 4.56 (t, 1H), 3.63 (m, 2H), 3.45(m, 2H), 2.34 (s, 3H), 2.22-2.77 (m, 9H), 1.81 (m, 2H), 1.20 (m, 3H),1.05 (m, 6H), 0.74 (m, 3H). A-9 

δ_(H) 6.93 (2H, s), 5.70 (1H, br. s), 3.96 (2H, dd, J = 11.2, 3.6 Hz),3.42-3.35 (2H, m), 2.65-2.60 (2H, m), 2.39-2.34 (2H, m), 2.28 (3H, s),2.24-2.17 (1H, m), 2.06 (3H, s), 2.03 (3H, s), 1.69-1.60 (3H, m),1.33-1.24 (4H, m). A-10

δ_(H) 6.92-6.91 (2H, m), 5.97 (1H, br. s), 4.00-3.97 (2H, m), 3.41-3.33(2H, m), 2.59-2.49 (2H, m), 2.35-2.30 (2H, m), 2.27 (3H, s), 2.06 (3H,s), 2.02 (3H, s), 1.59-1.33 (7H, m), 0.93 (3H, dd). A-11

δ_(H) 7.00 (2H, s), 5.50 (1H, br. s), 3.98 (2H, dd), 3.40 (2H, t, J =11.3 Hz), 2.68-2.64 (2H, m), 2.39-2.31 (9H, m), 1.67-1.60 (4H, m),1.45-1.42 (2H, m), 1.34-1.25 (2H, m), 1.08 (6H). A-12

δ_(H) 7.00 (2H, s), 5.59 (1H, br. s), 4.02- 3.99 (2H, m), 3.42-3.35 (2H,m), 2.66- 2.53 (4H, m), 2.44-2.28 (6H, m), 1.68- 1.50 (4H, m), 1.44-1.37(3H, m), 1.27- 1.23 (3H, m), 1.09 (6H, q), 0.95 (3H, dd). A-13

δ_(H) 7.55-7.52 (1H, m), 7.49-7.47 (2H, m), 7.42 (1H, dd), 7.39-7.36(2H, m), 7.23 (1H, dd), 4.02-4.00 (2H, m), 3.43- 3.35 (2H, m), 2.60-2.24(6H, m), 1.65- 1.37 (5H, m), 1.15 (3H, q), 0.95 (3H, dd). A-14

δ_(H) 6.75 (s, 2H), 2.59 (m, 6H), 2.20 (m, 10H), 1.93 (m, 2H), 1.36 (m,1H), 1.27 (m, 2H), 1.21 (m, 2H), 0.92 (2t, 6H). A-15

δ_(H) 7.49-4.47 (2H, m), 7.45-7.42 (1H, m), 7.39-7.36 (2H, m), 7.26-7.18(2H, m), 4.02-3.99 (2H, m), 3.40-3.35 (2H, m), 2.26-2.53 (2H, m),2.41-2.34 (2H, m), 2.14 (3H, s), 1.66-1.50 (5H, m), 1.41-1.35 (2H, m),0.95-0.91 (3H, m). A-16

δ_(H) 6.99 (s, 2H), 5.64 (br s, 1H), 3.36 (m, 1H), 3.03 (m, 1H), 2.66(m, 2H), 2.33 (m, 10H), 2.15 (m, 2H), 1.62, (m, 4H), 1.43 (m, 3H), 1.09(2t, 6H). A-17

δ_(H) 6.99 (s, 2H), 5.56 (br s, 1H), 3.06 (m, 4H), 2.66 (m, 2H), 2.33(m, 10H), 2.12 (m, 2H), 1.90 (m, 2H), 1.68 (m, 1H), 1.51 (m, 2H), 1.06(m, 6H). A-18

δ_(H) 6.98 (s, 2H), 5.74 (s, 1H), 3.99-3.94 (m, 2H), 3.93-3.87 (m, 1H),3.80-3.71 (m, 1H), 2.67-2.16 (m, 15H), 1.66-1.53 (m, 2H), 1.10-1.05 (m,6H), 1.01 (dd, 1H), 0.94 (d, 1H). A-19

δ_(H) 7.00 (s, 2H), 5.50 (brs, 1H), 3.98 (dd, 2H), 3.40 (t, 2H),2.46-2.18 (m, 6H), 2.63 (q, 4H), 1.74-1.50 (m, 6H), 1.45 (t, 1H),1.40-1.30 (m, 1H), 1.25 (t, 3H), 1.09 (t, 3H), 1.07 (t, 3H). A-20

δ_(H) 7.54 (d, 1H), 7.48 (d, 2H), 7.42 (dd, 1H), 7.38 (d, 2H), 7.23 (dd,1H), 5.75-5.57 (m, 1H), 3.98 (d, 2H), 3.40 (t, 2H), 2.75-2.59 (m, 2H),2.47 (q, 2H), 2.54-2.32 (m, 2H), 2.32-2.16 (m, 1H), 1.78-1.51 (m, 4H),1.51-1.40 (m, 1H), 1.40-1.24 (m, 2H), 1.15 (q, 3H). A-21

δ_(H) 7.30 (dd, 1H), 7.12 (s, 1H), 6.91 (d, 1H), 6.21 (brs, 1H), 3.97(dd, 2H), 3.79 (s, 3H), 3.39 (t, 2H), 2.63 (t, 2H), 2.42-2.26 (m, 2H),2.26-2.15 (m, 1H), 1.73-1.52 (m, 6H), 1.37-1.27 (m, 1H). A-22

δ_(H) 7.47 (d, 2H), 7.51-7.43 (m, 1H), (7.36 (d, 2H), 7.40-7.28 (m, 1H),7.23 (dd, 1H), 6.33 (brs, 1H), 3.94 (dd, 2H), 3.36 (t, 2H), 2.62 (d,2H), 2.44-2.14 (m, 3H), 2.15 (s, 1.5H), 2.11 (s, 1.5H), 1.70-1.56 (m,3H), 1.44-1.35 (m, 2H), 1.35-1.21 (m, 2H). A-23

δ_(H) 7.30-7.20 (m, 2H), 7.06 (s, 1H), 5.62 (s, 0.5H), 5.57 (s, 0.5H),3.96 (dd, 2H), 3.39 (t, 2H), 2.63 (dt, 2H), 2.44-2.30 (m, 2H), 2.26-2.14(m, 1H), 2.10 (s, 1.5H), 2.07 (s, 1.5H), 1.72-1.49 (m, 3H), 1.41 (t,2H), 1.37-1.24 (m, 2H). A-24

δ_(H) 7.49 (dt, 1H), 7.45 (d, 2H), 7.34 (dd, 1H), 7.23-7.27 (m, 1H),7.21 (d, 2H), 6.07 (brs, 1H), 3.95 (dd, 2H), 3.37 (t, 2H), 2.57- 2.68(m, 2H), 2.38 (s, 3H), 2.29-2.42 (m, 2H), 2.15-2.27 (m, 1H), 1.56-1.71(m, 3H), 2.11 (s, 1.5H), 2.15 (s, 1.5H), 1.36-1.44 (m, 2H), 1.21-1.36(m, 2H). A-25

δ_(H) 7.55 (dd, 1H), 7.43 (d, 2H), 7.33 (d, 1H), 7.21 (d, 2H), 7.03 (d,1H), 3.96 (dd, 2H), 3.82 (s, 3H), 3.38 (t, 2H), 2.70-2.58 (m, 2H),2.42-2.32 (m, 2H), 2.37 (s, 3H), 2.43- 2.32 (m, 1H), 1.71-1.57 (m, 3H),1.40 (t, 2H), 1.36-1.23 (m, 2H). A-26

δ_(H) 8.13 (dd, 1H), 7.60 (dt, 1H), 7.49 (dt, 1H), 7.39 (dd, 1H), 7.06(t, 1H), 6.95 (td, 1H), 4.02-3.92 (m, 2H), 3.95 (s, 3H), 3.39 (t, 2H),2.72-2.56 (m, 2H), 2.46-2.31 (m, 2H), 2.29-2.19 (m, 1H), 2.17 (d, 3H),1.73- 1.58 (m, 3H), 1.47-1.38 (m, 2H), 1.38- 1.24 (m, 2H). A-27

δ_(H) 8.09 (dd, 1H), 7.61 (d, 1H), 7.56-7.45 (m, 1H), 7.41-7.34 (m, 1H),7.07 (t, 1H), 6.93 (td, 1H), 4.25-4.10 (m, 2H), 3.98 (dd, 2H), 3.39 (t,2H), 2.72-2.57 (m, 2H), 2.46- 2.32 (m, 2H), 2.29-2.19 (m, 1H), 2.17 (d,3H), 1.85-1.52 (m, 6H), 1.48-1.38 (m, 4H), 1.38-1.19 (m, 2H). A-28

δ_(H) 7.57 (d, 1H), 7.49-7.36 (m, 1H), 7.24- 7.14 (m, 1H), 7.02 (t, 1H),6.84 (dd, 1H), 6.78 (td, 1H), 5.65 (s, 0.5H, CH), 5.60 (s, 0.5H, CH),3.99 (dd, 2H), 3.41 (t, 2H), 2.74-2.61 (m, 2H), 2.47-2.33 (m, 2H),2.30-2.20 (m, 1H), 2.17 (d, 3.0H), 1.73- 1.24 (m, 7H). A-29

δ_(H) 7.56 (d, 2H), 7.49 (td, 1H), 7.39 (d, 1H), 7.26-7.22 (m, 3H), 5.73(brs, 0.5H), 5.67 (brs, 0.5H), 3.98 (dd, 2H), 3.40 (t, 2H), 2.73-2.59(m, 2H), 2.47-2.33 (m, 2H), 2.29-2.20 (m, 1H), 2.17 (d, 3H,), 1.64 (d,3H), 1.43 (t, 2H), 1.39-1.24 (m, 2H). A-30

δ_(H) 7.79 (s, 1H), 7.73 (d, 1H), 7.61-7.50 (m, 3H), 7.41 (d, 1H), 7.30(t, 1H), 5.68 (brs, 0.5H), 5.63 (brs, 0.5H), 3.98 (dd, 2H), 3.40 (t,2H), 2.74-2.57 (m, 2H), 2.48-2.32 (m, 2H), 2.30-2.20 (m, 1H), 2.18 (d,3H), 1.65 (d, 3H), 1.44 (t, 2H), 1.39-1.23 (m, 2H). A-31

δ_(H) 7.34 (s, 2H), 7.29-7.23 (m, 1H), 7.05- 7.01 (m, 1H), 5.63 (brs,0.5H), 5.57 (brs, 0.5H), 3.97 (dd, 2H), 3.40 (td, 2H), 2.71- 2.58 (m,2H), 2.51-2.31 (m, 4H), 2.28- 2.15 (m, 1H), 1.73-1.58 (m, 3H), 1.46-1.39 (m, 2H), 1.38-1.26 (m, 2H), 1.11 (q, 3H). A-32

δ_(H) 7.77 (s, 1H), 7.71 (d, 1H), 7.60-7.45 (m, 3H), 7.36 (d, 1H), 6.97(d, 1H), 5.95 (brs, 1H), 3.98-3.90 (m, 2H), 3.85 (s, 3H), 3.35 (td, 2H),2.62-2.55 (m, 2H), 2.55-2.45 (m, 1H), 2.36 (d, 2H), 1.70-1.39 (m, 3H),1.33- 1.19 (m, 4H). A-33

δ_(H) 7.49 (d, 2H), 7.35 (s, 2H), 7.26 (d, 2H), 5.58 (s, 1H), 3.98 (m,dd, 2H), 3.4 (m, 2H), 2.68 (m, 2H), 2.45 (m, 9H), 2.27 (m, 1H), 1.65 (m,3H), 1.43 (t, 2H), 1.3 (m, 2H), 1.12 (m, 6H). A-34

δ_(H) 7.52 (dd, 2H), 7.4 (dd, 2H), 7.33 (s, 2H), 5.52 (s, 1H), 3.98 (m,2H), 3.4 (m, 2H), 2.69 (m, 2H), 2.45 (m, 6H), 2.27 (m, 1H), 1.65 (m,3H), 1.45 (t, 2H), 1.33 (m, 2H), 1.13 (m, 6H). A-35

δ_(H) 7.69 (dd, 4H), 7.38 (s, 2H), 5.52 (s, 1H), 3.98 (m, 2H), 3.41 (m,2H), 2.7 (m, 2H), 2.45 (m, 6H), 2.28 (m,1H), 1.65 (m, 3H), 1.46 (m, 2H),1.33 (m, 2H), 1.15 (m, 6H). A-36

δ_(H) 7.5 (dd, 2H), 7.36 (s, 2H), 7.28 (d, 2H), 5.62 (s, 1H), 4.03 (m,2H), 3.42 (m, 2H), 2.72 (m, 2H), 2.45 (m, 2H), 2.43 (s, 3H), 2.3 (m,1H), 2.22 (s, 3H), 2.19 (s, 3H), 1.69 (m, 3H), 1.49 (m, 2H), 1.37 (m,2H). A-37

δ_(H) 7.54 (d, 2H), 7.44 (d, 2H) 7.32 (s, 2H), 5.6 (s, 1H), 4.02 (m,2H), 3.43 (m, 2H), 2.72 (m, 2H), 2.45 (m, 2H), 2.3 (m, 1H), 2.22 (s,3H), 2.19 (s, 3H), 1.69 (m, 3H), 1.5 (m, 2H), 1.37 (m, 2H). A-38

δ_(H) 7.67 (dd, 4H), 7.33 (s, 2H), 5.5 (s, 1H), 3.98 (m, 2H), 3.4 (m,2H), 2.68 (m, 2H), 2.42 (m, 2H), 2.25 (m, 1H), 2.17 (s, 3H), 2.15 (s,3H), 1.65 (m, 3H), 1.45 (m, 2H), 1.33 (m, 2H). A-39

δ_(H) 7.49 (q, 2H), 7.44 (d, 1H), 7.32 (d, 1H), 7.17 (d, 1H), 7.08 (t,2H), 6.36 (brs, 1H), 3.93 (dd, 2H), 3.35 (t, 2H), 2.61 (d, 2H),2.41-2.27 (m, 2H), 2.24-2.15 (m, 1H), 2.13 (d, 3H), 1.69-1.55 (m, 3H),1.42- 1.35 (m, 2H), 1.35-1.20 (m, 2H). A-40

δ_(H) 7.42 (d, 1H), 7.34 (d, 2H), 7.29-7.22 (m, 1H), 7.22-7.12 (m, 2H),6.15 (brd, 1H), 3.94 (dd, 2H), 3.37 (t, 2H), 2.63 (td, 2H), 2.42-2.30(m, 2H), 2.26-2.15 (m, 1H), 2.14 (d, 3H), 1.72-1.57 (m, 3H), 1.44- 1.37(m, 2H), 1.37-1.22 (m, 2H). A-41

δ_(H) 7.57 (d, 2H), 7.53 (t, 2H), 7.36-7.32 (m, 3H), 5.74 (s, 1H), 3.96(dd, 2H), 3.39 (ddt, 2H), 2.70-2.65 (m, 2H), 2.45-2.20 (m, 3H), 2.17 (s,3H), 2.14 (s, 3H), 1.75-1.50 (m, 3H), 1.45-1.20 (m, 4H). A-42

δ_(H) 7.52 (dt, 1H), 7.48 (d, 2H), 7.36 (dd, 1H), 7.30-7.22 (m, 3H),5.77 (brs, 0.5H), 5.71 (brs, 0.5H), 3.98 (dd, 2H), 3.40 (t, 2H), 2.68(q, 2H), 2.73-2.60 (m, 2H), 2.45- 2.34 (m, 2H), 2.29-2.19 (m, 1H), 2.17(s, 1.5H), 2.13 (s, 1.5H), 1.74-1.56 (m, 3H), 1.43 (t, 2H), 1.39-1.23(m, 2H), 1.26 (t, 3H). A-43

δ_(H) 7.52 (td, 1H), 7.46 (d, 2H), 7.36 (dd, 1H), 7.28 (d, 1H), 7.18 (d,2H), 5.79 (brs, 0.5H), 5.73 (brs, 0.5H), 3.98 (dd, 2H), 3.40 (t, 2H),2.72-2.60 (m, 2H), 2.50 (d, 2H), 2.45-2.34 (m, 2H), 2.30-2.20 (m, 1H),2.16 (s, 1.5H), 2.14 (s, 1.5H), 1.88 (quintet, 1H), 1.78-1.59 (m, 3H),1.43 (t, 2H), 1.39-1.26 (m, 2H), 0.92 (d, 6H). A-44

δ_(H) 7.53 (t, 1H), 7.49 (d, 2H), 7.43 (d, 2H), 7.37 (dd, 1H), 7.30-7.27(m, 1H), 5.75 (s, 0.5H), 5.69 (s, 0.5H), 3.98 (dd, 2H), 3.40 (t, 2H),2.71-2.60 (m, 2H), 2.44-2.34 (m, 2H), 2.29-2.20 (m, 1H), 2.17 (s, 1.5H),2.15 (s, 1.5H), 1.69-1.56 (m, 3H), 1.43 (t, 2H), 1.35 (s, 9H), 1.38-1.27(m, 2H). A-45

δ_(H) 7.33 (m, 1H), 7.33-7.55 (m, 6H), 5.63 (m, 1H), 4.99 (m, 1H), 4.02(m, 2H), 3.90 (m, 2H), 2.27-2.84 (m, 7H), 1.85 (m, 2H), 1.15 (m, 3H).A-46

δ_(H) 7.48 (m, 3H), 7.38 (m, 3H), 7.25 (m, 1H), 5.63-5.69 (m, 1H), 4.98(m, 1H), 4.01 (m, 2H), 3.88 (m, 2H), 2.23-2.85 (m, 5H), 2.13-2.18 (m,3H), 1.85 (m, 2H). A-47

δ_(H) 7.49 (dt, 1H), 7.42-7.39 (m, 1H), 7.37 (d, 2H), 7.30 (dd, 1H),7.25-7.22 (m, 1H), 5.80-5.16 (brs, 1H), 4.03 (dd, 2H), 3.44 (t, 2H),2.70 (d, 2H), 2.42 (s, 3H,), 2.47-2.31 (m, 3H), 2.16 (s, 1.5H), 2.13 (s,1.5H), 1.71-1.61 (m, 3H), 1.49-1.41 (m, 2H), 1.40-1.28 (m, 2H). A-48

δ_(H) 7.50-7.44 (m, 1H), 7.39-7.29 (m, 3H), 7.24-7.21 (m, 1H), 7.06-7.00(m, 1H), 5.86-5.59 (m, 1H), 4.03-3.96 (m, 2H), 3.41 (t, 2H), 2.72-2.61(m, 2H), 2.45-2.36 (m, 2H), 2.32 (s, 3H), 2.30-2.21 (m, 1H), 2.17 (s,1.5H), 2.13 (s, 1.5H), 1.70-1.60 (m, 3H), 1.47-1.40 (m, 2H), 1.39-1.29(m, 2H). A-49

δ_(H) 7.67-7.22 (m, 6H), 6.02-5.57 (s, 1H), 4.07-3.98 (m, 2H), 3.44 (t,2H), 2.70 (d, 2H), 2.49-2.20 (m, 3H), 2.19 (s, 1.5H), 2.16 (s, 1.5H),1.75-1.60 (m, 3H), 1.49- 1.41 (m, 2H), 1.41-1.27 (m, 2H). A-50

δ_(H) 7.51-7.45 (m, 3H), 7.38-7.33 (m, 1H), 7.25-7.21 (m, 1H), 7.08 (dd,2H), 5.83- 5.64 (m, 1H), 5.21 (s, 2H), 3.99 (dd, 2H), 3.50 (s, 3H), 3.41(t, 2H), 2.72-2.61 (m, 2H), 2.45-2.34 (m, 2H), 2.29-2.19 (m, 1H), 2.16(s, 1.5H), 2.13 (s, 1.5H), 1.70- 1.60 (m, 3H), 1.46-1.40 (m, 2H), 1.38-1.29 (m, 2H). A-51

δ_(H) 7.82-7.73 (m, 2H), 7.48-7.37 (m, 2H), 7.31-7.18 (m, 2H), 5.70-5.25(s, 1H), 4.07- 3.96 (m, 2H), 3.43 (t, 2H), 2.76-2.62 (m, 2H), 2.49-2.25(m, 3H), 2.17 (s, 1.5H), 2.15 (s, 1.5H), 1.75-1.59 (m, 3H), 1.50- 1.40(m, 2H), 1.39-1.29 (m, 2H). A-52

δ_(H) 8.30-8.21 (m, 1H), 7.74-7.65 (m, 1H), 7.35 (d, 1H), 7.48 (dt, 1H),7.31-7.27 (m, 1H), 7.20-7.15 (m, 1H), 6.87 (brd, 1H), 6.73 (brs, 1H),5.66-5.04 (brs, 1H), 3.97 (dt, 2H), 3.39 (t, 2H), 2.67 (dd, 2H), 2.49-2.24 (m, 3H), 2.17 (s, 1.5H), 2.14 (s, 1.5H), 1.74-1.59 (m, 3H),1.50-1.42 (t, 2H), 1.38-1.28 (m, 2H). A-53

δ_(H) 7.44 (d, 1H), 7.34 (d, 1H), 7.22-7.08 (m, 2H), 7.04-6.98 (m, 1H),6.85 (d, 1H), 5.99 (s, 2H), 5.06-4.60 (brs, 1H), 4.05- 3.91 (m, 2H),3.47-3.30 (m, 2H), 2.72- 2.53 (m, 2H), 2.52-2.26 (m, 3H), 2.19 (s, 3H),1.73-1.50 (m, 3H), 1.50-1.39 (m, 2H), 1.32-1.18 (m, 2H). A-54

δ_(H) 7.26-7.19 (m, 2H), 7.09-7.01 (m, 2H), 6.90-6.80 (m, 3H), 4.27 (d,4H), 3.98 (dd, 2H), 3.40 (t, 2H), 2.70-2.58 (m, 2H), 2.42- 2.17 (m, 3H),2.09 (s, 1.5H), 2.05 (s, 1.5H), 1.72-1.57 (m, 3H), 1.46-1.38 (m, 2H),1.37-1.23 (m, 2H). A-55

δ_(H) 7.50 (m, 3H), 7.39 (m, 3H), 7.25 (m, 1H) 5.70 (br, 1H), 4.68 (m,1H), 4.13 (m, 2H), 3.80 (m, 2H), 2.20-2.80 (m, 5H), 2.13-2.16 (m, 3H),2.10 (m, 1H), 1.77 (m, 2H), 1.36 (m, 1H). A-56

δ_(H) 7.48 (m, 3H), 7.37 (m, 3H), 7.24 (m, 1H), 5.62 (br, 1H), 4.58 (m,1H), 3.60 (m, 2H), 3.44 (m, 2H), 2.20-2.81 (m, 5H), 2.13- 2.18 (m, 3H),1.82 (m, 2H), 1.21 (s, 3H), 0.75 (s, 3H). A-57

δ_(H) 7.48 (m, 3H), 7.38 (m, 3H), 7.23 (m, 1H), 5.62 (br, 1H), 4.55 (m,1H), 2.82 (m, 2H), 2.40 (m, 2H), 2.20-2.80 (m, 5H), 2.14- 2.19 (m, 3H),1.80 (m, 2H), 1.73 (m, 2H), 1.10 (m, 2H), 0.88 (m, 3H), 0.80 (m, 3H).A-58

δ_(H) 7.48 (m, 3H), 7.39 (m, 3H), 7.24 (m, 1H), 5.72 (br, 1H), 5.14 (m,1H), 3.60-3.90 (m, 6H), 2.23-2.85 (m, 5H), 2.16-2.20 (m, 3H), 1.87 (m,2H), 1.73 (m, 4H), 1.10 (m, 2H). A-59

δ_(H) 7.49 (m, 3H), 7.37 (m, 3H), 7.25 (m, 1H), 5.68 (br, 1H), 5.02-5.09(m, 1H), 3.40-4.00 (m, 7H) 2.22-2.84 (m, 5H), 2.13- 2.19 (m, 3H),1.42-1.90 (m, 7H). A-60

δ_(H) 7.48 (m, 3H), 7.35 (m, 3H), 7.22 (m, 1H), 5.70 (br, 1H), 5.01-5.14(m, 1H), 3.35- 4.18 (m, 7H), 2.20-2.85 (m, 5H), 2.13-2.18 (m, 3H),1.25-1.90 (m, 9H). A-61

δ_(H) 7.48 (m, 3H), 7.36 (m, 3H), 7.23 (m, 1H), 5.72 (br, 1H), 5.00 (m,1H), 3.42-4.10 (m, 6H), 2.23-2.88 (m, 5H), 2.14-2.19 (m, 3H), 1.90 (m,2H). A-62

δ_(H) 7.46 (m, 3H), 7.35 (m, 3H), 7.23 (m, 1H), 5.70 (br, 1H), 4.84 (m,1H), 3.91 (m, 2H), 3.65 (m, 2H), 2.20-2.80 (m, 5H), 2.15- 2.19 (m, 3H),1.73 (m, 6H). A-63

δ_(H) 7.48 (m, 3H), 7.38 (m, 3H), 7.24 (m, 1H), 5.75 (br, 1H), 5.02-5.12(m, 1H), 3.42 (s, 3H), 3.42-4.35 (m, 5H), 2.24-2.83 (m, 5H), 2.14-2.19(m, 3H), 1.86 (m, 2H). A-64

δ_(H) 7.48 (m, 3H), 7.36 (m, 3H), 7.23 (m, 1H), 5.74 (br, 1H), 4.09-4.66(m, 1H), 3.25- 4.06 (m, 4H), 2.20-2.80 (m, 5H), 2.13-2.18 (m, 3H), 2.10(m, 1H), 1.79 (m, 2H). 1.30- 0.72 (2xd, 3H). A-65

δ_(H) 7.47 (m, 3H), 7.36 (m, 3H), 7.23 (m, 1H), 5.73 (br, 1H), 4.74 (m,1H), 4.12 (m, 2H), 3.25 (m, 2H), 2.21-2.80 (m, 5H), 2.13- 2.19 (m, 3H),1.85 (m, 2H), 0.71 (m, 2H), 0.35 (m, 2H).

Example 6 Preparation of 2,2-dimethylpropionic acid3-oxo-5-(tetrahydrofuran-3-ylmethyl)-2-(2,4,6-trimethylphenyl)cyclohex-1-enylEster

A solution of trimethylacetyl chloride (55 mg, 0.457 mmol) indichloromethane (2 ml) is added dropwise to a solution of2-(2,4,6-trimethylphenyl)-5-(tetrahydrofuran-3-ylmethyl)-cyclohexane-1,3-dione(120 mg, 0.38 mmol) in dichloromethane (2 ml) and the mixture is cooledin an ice bath and stirred at 0° C. for 2 minutes. A solution oftriethylamine (46 mgs, 0.457 mmol) in dichloromethane (1 ml) is added,and once the addition is complete the cooling bath is removed and thereaction mixture is stirred at room temperature for 2 hours. The mixtureis diluted with dichloromethane (20 ml) and washed with saturatedaqueous sodium bicarbonate solution (3×20 ml). The organic phase isdried over anhydrous magnesium sulfate, filtered and the filtrate isconcentrated in vacuo. The residue is purified by column chromatographyon silica gel to give 2,2-dimethylpropionic acid3-oxo-5-(tetrahydrofuran-3-ylmethyl)-2-(2,4,6-trimethylphenyl)cyclohex-1-enylester as a white solid, m.p. 108-110° C.

¹H NMR (CDCl₃, ppm) 66.81 (s, 2H), 3.94 (q, 1H), 3.88 (m, 1H), 3.77 (m,1H), 3.35 (m, 1H), 2.77-2.66 (m, 2H), 2.62-2.52 (m, 1H), 2.40-2.29 (m,3H), 2.22 (s, 3H), 2.15-2.05 (m, 1H), 2.03 (s, 3H), 1.99 (s, 3H),1.61-1.53 (m, 3H), 0.88 (s, 9H)

Experimental procedures to key intermediates.

Example 1A Preparation of 5-(4-chlorophenyl)-2-methylphenylboronic AcidStep 1

4-Chlorophenylboronic acid (20.2 g, 0.13 mol) andtetrakis(triphenylphosphine)palladium (0) (3.7 g, 0.003 mol) are addedto a solution of 5-bromo-2-methylaniline (20 g, 0.1 mol) in1,2-dimethoxyethane (200 ml). After stirring the reaction mixture for 15minutes at 20° C., a solution of 20% aqueous sodium carbonate (300 ml)is added to the mixture, and the resulting mixture is refluxed for 24hours. The reaction mixture is cooled to room temperature, diluted withwater (600 ml) and extracted using ethyl acetate. The combined organicextracts are dried over anhydrous sodium sulfate, filtered and thefiltrate evaporated in vacuo. The residue is further purified by columnchromatography on silica gel, eluting with 7% ethyl acetate in hexane togive 5-(4-chlorophenyl)-2-methylaniline (21.0 g).

Step 2

Hydrobromic acid (48% wt. in water, 120 ml) is added dropwise to asuspension of 5-(4-chlorophenyl)-2-methylaniline (21 g, 0.09 mol) inwater (80 ml), and the mixture stirred until the solid is dissolved. Themixture is cooled to −5° C. and a solution of sodium nitrite (10.12 g,0.14 mol) in water (50 ml) is added dropwise, maintaining thetemperature at 0-5° C. The reaction mixture is stirred for 1 hour, thenadded to a pre-cooled solution of cuprous bromide (17.9 g, 0.12 mol) inhydrobromic acid (48% wt. in water, 120 ml) at 0° C. The reactionmixture is stirred and allowed to warm to room temperature overnight.The mixture is extracted with ethyl acetate, and the organic extractsare combined, dried over anhydrous sodium sulfate, filtered and thefiltrate concentrated in vacuo. The residue is further purified bycolumn chromatography on silica gel, eluting with 2% ethyl acetate inhexane to give 5-(4-chlorophenyl)-2-methyl-1-bromobenzene (15.0 g).

Step 3

5-(4-chlorophenyl)-2-methyl-1-bromobenzene (5.0 g, 0.02 mol) isdissolved in THF (125 ml), and the temperature temperature is brought to−78° C. n-Butyllithium (1.33 molar solution in hexanes, 17.3 ml,) isadded dropwise over 30 minutes, maintaining the temperature at around−78° C. The reaction mixture is stirred for one and half hours at −78°C., then trimethylborate (2.58 g, 0.024 mol) is added dropwise and thereaction mixture stirred for three and half hours, allowing it to warmto 0° C. A solution of 2N aqueous hydrochloric acid (50 ml) is thenadded dropwise, and once the addition is complete the mixture is stirredfor 2 hours. The mixture is concentrated in vacuo to remove most of thetetrahydrofuran, then diluted with water (˜80 ml) and extracted withdiethyl ether. The organic extracts are combined, dried over anhydroussodium sulfate, filtered and the filtrate evaporated in vacuo. Theresidue is further purified by flash column chromatography on silicagel, eluting with 7% ethyl acetate in hexane to give5-(4-chlorophenyl)-2-methylphenylboronic acid (2.5 g).

Example 1B Preparation of 5-(4-chlorophenyl)-2-ethylphenylboronic AcidStep 1

Ammonium nitrate (39.6 g, 0.49 mol) is added portionwise to a chilled(ice-bath) solution of 4-ethylaniline (20 g, 0.16 mol) in concentratedsulfuric acid (100 ml, maintaining the temperature −10° to 0° C. byexternal cooling. The reaction mixture is stirred for two hours, thenpoured onto crushed ice, and the precipitate is collected by filtration.The solid is taken up in water, the solution made neutral by addition ofdilute aqueous sodium hydroxide solution and the extracted with ethylacetate. The organic extracts are combined, dried over anhydrous sodiumsulfate, filtered and the filtrate evaporated in vacuo to give4-ethyl-3-nitroaniline (20 g).

Step 2

Hydrobromic acid (48% wt. in water, 240 ml) is added dropwise to asuspension of 4-ethyl-3-nitroaniline (20 g, 0.12 mol) in water (80 ml),and the mixture stirred until the solid is dissolved. The mixture iscooled to −5° C. and a solution of sodium nitrite (19.8 g, 0.28 mol) inwater (100 ml) is added dropwise, maintaining the temperature at 0-5° C.Once the addition is complete, the cooling bath is removed and thereaction mixture is stirred for one hour at room temperature. Themixture is added dropwise to a pre-cooled solution of cuprous bromide(22.4 g, 0.16 mol) in hydrobromic acid (48% wt. in water) at 0° C. Thereaction mixture is stirred and allowed to warm to room temperature overthree hours. The mixture is extracted with diethyl ether, and theorganic extracts are combined, dried over anhydrous sodium sulfate,filtered and the filtrate concentrated in vacuo. The residue is furtherpurified by column chromatography on silica gel, eluting with hexane togive 4-bromo-1-ethyl-2-nitrobenzene (18 g)

Step 3

A solution of ammonium chloride (12.5 g, 0.2 mol) in water (30 ml) isadded to a mixture of zinc dust (35.7 g, 0.5 mol) and4-bromo-1-ethyl-2-nitrobenzene (18 g, 0.07 mol) in methanol (720 ml) andwater (180 ml). The reaction mixture is refluxed for one hour, thencooled to room temperature and filtered through a plug of diatomaceousearth. The filtrate is concentrated in vacuo, then diluted with waterand extracted with ethyl acetate. The combined organic extracts arewashed with water and brine, dried over anhydrous sodium sulfate,filtered and the filtrate concentrated in vacuo to yield5-bromo-2-ethylaniline (14 g), used without further purification in thenext step.

Step 4

4-Chlorophenylboronic acid (13.2 g, 0.08 mol) andtetrakis(triphenylphosphine) palladium (0) (2.4 g, 0.002 mol) are addedto a solution of 5-bromo-2-ethylaniline (14.1 g, 0.07 mol) in1,2-dimethoxyethane (140 ml). After stirring the reaction mixture for 15minutes at 20° C., a solution of 20% aqueous sodium carbonate (300 ml)is added to the mixture, and the resulting mixture is refluxed for 24hours. The reaction mixture is cooled to room temperature, diluted withwater and extracted using ethyl acetate. The combined organic extractsare dried over anhydrous sodium sulfate, filtered and the filtrateevaporated in vacuo. The residue is further purified by columnchromatography on silica gel, eluting with 5% ethyl acetate in hexane togive 5-(4-chlorophenyl)-2-ethylaniline (14.3 g).

Step 5

Hydrobromic acid (48% wt. in water, 85 ml) is added dropwise to asuspension of 5-(4-chlorophenyl)-2-ethylaniline (14.3 g, 0.05 mol) inwater (57 ml), and the mixture stirred. The mixture is cooled to −5° C.and a solution of sodium nitrite (5.07 g, 0.072 mol) in water (25 ml) isadded dropwise, maintaining the temperature at 0-5° C. The reactionmixture is stirred for 1 hour, then added to a pre-cooled solution ofcuprous bromide (9 g, 0.062 mol) in hydrobromic acid (48% wt. in water,64 ml) at 0° C. The reaction mixture is stirred and allowed to warm toroom temperature overnight. The mixture is diluted with water, extractedwith diethyl ether, and the organic extracts are combined, dried overanhydrous sodium sulfate, filtered and the filtrate concentrated invacuo. The residue is further purified by column chromatography onsilica gel, eluting with 2% ethyl acetate in hexane to give5-(4-chlorophenyl)-2-ethyl-1-bromobenzene (10 g).

Step 6

5-(4-chlorophenyl)-2-ethyl-1-bromobenzene (10 g, 0.03 mol) is dissolvedin THF (250 ml), and the temperature is brought to −78° C.n-Butyllithium (1.33 molar solution in hexanes, 34.6 ml,) is addeddropwise over 30 minutes, maintaining the temperature at around −78° C.The reaction mixture is stirred for one and half hours, thentrimethylborate (4.9 g, 0.05 mol) is added dropwise and the reactionmixture stirred for two hours. A solution of 2N aqueous hydrochloricacid (100 ml) is added dropwise, and once the addition is complete themixture is stirred for two hours. The mixture is concentrated to removemost of the tetrahydrofuran, then diluted with water and extracted withdiethyl ether. The organic extracts are washed with water and brine,combined, dried over anhydrous sodium sulfate, filtered and the filtrateevaporated in vacuo. The residue is further purified by flash columnchromatography on silica gel, eluting with 7% ethyl acetate in hexane togive 5-(4-chloro-phenyl)-2-methylphenylboronic acid (5.4 g).

Specific examples of the compounds of the invention include thosecompounds detailed in Table 1 to Table 81.

Table 1 covers 232 compounds of the following type

where G, R⁵, R⁶ and R⁷ are all hydrogen, and R¹, R², R³ and R⁴ are asdescribed in Table 1 below:

Compound Number R¹ R² R³ R⁴ 1.001 CH₃ H H H 1.002 CH₃ CH₃ H H 1.003 CH₃H CH₃ H 1.004 CH₃ H H CH₃ 1.005 CH₃ CH₃ CH₃ H 1.006 CH₃ CH₃ H CH₃ 1.007CH₃ CH₃ CH₃ CH₃ 1.007 CH₃ Cl H H 1.008 CH₃ Cl H CH₃ 1.009 CH₃ Cl H OCH₃1.010 CH₃ H Cl H 1.011 CH₃ H H Cl 1.012 CH₃ CH₃ Cl H 1.013 CH₃ CH₃ H Cl1.014 CH₃ H Cl CH₃ 1.015 CH₃ CH₃ Cl CH₃ 1.016 CH₃ Br H H 1.017 CH₃ Br HCH₃ 1.018 CH₃ Br H OCH₃ 1.019 CH₃ H Br H 1.020 CH₃ H H Br 1.021 CH₃ CH₃Br H 1.022 CH₃ CH₃ H Br 1.023 CH₃ H Br CH₃ 1.024 CH₃ CH₃ Br CH₃ 1.025CH₃ CH₃O H H 1.026 CH₃ CH₃O H CH₃ 1.027 CH₃ CH₃O H Cl 1.028 CH₃ CH₃O HBr 1.029 CH₃ CH₃CH₂O H H 1.030 CH₃ CH₃CH₂O H CH₃ 1.031 CH₃ CH₃CH₂O H Cl1.032 CH₃ CH₃CH₂O H Br 1.033 CH₃ H CH₃O H 1.034 CH₃ H H CH₃O 1.035 CH₃CH₃ CH₃O H 1.036 CH₃ CH₃ H CH₃O 1.037 CH₃ H CH₃O CH₃ 1.038 CH₃ CH₃ CH₃OCH₃ 1.039 CH₃ —CH═CH₂ H CH₃ 1.040 CH₃ CH₃ H —CH═CH₂ 1.041 CH₃ —C•CH HCH₃ 1.042 CH₃ CH₃ H —C•CH 1.043 CH₃ —CH═CH₂ H —CH═CH₂ 1.044 CH₃ CH₂CH₃ HCH₃ 1.045 CH₃ phenyl H CH₃ 1.046 CH₃ 2-fluorophenyl H CH₃ 1.047 CH₃2-chlorophenyl H CH₃ 1.048 CH₃ 2-trifluoromethylphenyl H CH₃ 1.049 CH₃2-nitrophenyl H CH₃ 1.050 CH₃ 2-methylphenyl H CH₃ 1051 CH₃2-methanesulfonylphenyl H CH₃ 1.052 CH₃ 2-cyanophenyl H CH₃ 1.053 CH₃3-fluorophenyl H CH₃ 1.054 CH₃ 3-chlorophenyl H CH₃ 1.055 CH₃3-trifluoromethylphenyl H CH₃ 1.056 CH₃ 3-nitrophenyl H CH₃ 1.057 CH₃3-methylphenyl H CH₃ 1.058 CH₃ 3-methanesulfonylphenyl H CH₃ 1.059 CH₃3-cyanophenyl H CH₃ 1.060 CH₃ 4-fluorophenyl H CH₃ 1.061 CH₃4-chlorophenyl H CH₃ 1.062 CH₃ 4-trifluoromethylphenyl H CH₃ 1.063 CH₃4-nitrophenyl H CH₃ 1.064 CH₃ 4-methylphenyl H CH₃ 1.065 CH₃4-methanesulfonylphenyl H CH₃ 1.066 CH₃ 4-cyanophenyl H CH₃ 1.067 CH₃ Hphenyl H 1.068 CH₃ H 2-fluorophenyl H 1.069 CH₃ H 2-chlorophenyl H 1.070CH₃ H 2-trifluoromethylphenyl H 1.071 CH₃ H 2-nitrophenyl H 1.072 CH₃ H2-methylphenyl H 1.073 CH₃ H 2-methylsulfonylphenyl H 1.074 CH₃ H2-cyanophenyl H 1.075 CH₃ H 3-fluorophenyl H 1.076 CH₃ H 3-chlorophenylH 1.077 CH₃ H 3-trifluoromethylphenyl H 1.078 CH₃ H 3-nitrophenyl H1.080 CH₃ H 3-methylphenyl H 1.081 CH₃ H 3-methylsulfonylphenyl H 1.082CH₃ H 3-cyanophenyl H 1.083 CH₃ H 4-fluorophenyl H 1.084 CH₃ H4-chlorophenyl H 1.085 CH₃ H 4-trifluoromethylphenyl H 1.086 CH₃ H4-nitrophenyl H 1.087 CH₃ H 4-methylphenyl H 1.088 CH₃ H4-methylsulfonylphenyl H 1.089 CH₃ H 4-cyanophenyl H 1.090 CH₂CH₃ H H H1.091 CH₂CH₃ CH₃ H H 1.092 CH₂CH₃ H CH₃ H 1.093 CH₂CH₃ H H CH₃ 1.094CH₂CH₃ CH₃ CH₃ H 1.095 CH₂CH₃ CH₃ H CH₃ 1.096 CH₂CH₃ CH₃ CH₃ CH₃ 1.097CH₂CH₃ Cl H H 1.098 CH₂CH₃ Cl H CH₃ 1.099 CH₂CH₃ Cl H OCH₃ 1.100 CH₂CH₃H Cl H 1.101 CH₂CH₃ H H Cl 1.102 CH₂CH₃ CH₃ Cl H 1.103 CH₂CH₃ CH₃ H Cl1.104 CH₂CH₃ H Cl CH₃ 1.105 CH₂CH₃ CH₃ Cl CH₃ 1.106 CH₂CH₃ Br H H 1.107CH₂CH₃ Br H CH₃ 1.108 CH₂CH₃ Br H OCH₃ 1.109 CH₂CH₃ H Br H 1.110 CH₂CH₃H H Br 1.111 CH₂CH₃ CH₃ Br H 1.112 CH₂CH₃ CH₃ H Br 1.113 CH₂CH₃ H Br CH₃1.114 CH₂CH₃ CH₃ Br CH₃ 1.115 CH₂CH₃ CH₃O H H 1.116 CH₂CH₃ CH₃O H CH₃1.117 CH₂CH₃ CH₃O H Cl 1.118 CH₂CH₃ CH₃O H Br 1.119 CH₂CH₃ CH₃CH₂O H H1.120 CH₂CH₃ CH₃CH₂O H CH₃ 1.121 CH₂CH₃ CH₃CH₂O H Cl 1.122 CH₂CH₃CH₃CH₂O H Br 1.123 CH₂CH₃ H CH₃O H 1.124 CH₂CH₃ H H CH₃O 1.125 CH₂CH₃CH₃ CH₃O H 1.126 CH₂CH₃ CH₃ H CH₃O 1.127 CH₂CH₃ H CH₃O CH₃ 1.128 CH₂CH₃CH₃ CH₃O CH₃ 1.129 CH₂CH₃ —CH═CH₂ H CH₃ 1.130 CH₂CH₃ CH₃ H —CH═CH₂ 1.131CH₂CH₃ —C•CH H CH₃ 1.132 CH₂CH₃ CH₃ H —C•CH 1.133 CH₂CH₃ —CH═CH₂ H—CH═CH₂ 1.134 CH₂CH₃ CH₂CH₃ H CH₃ 1.135 CH₂CH₃ phenyl H CH₃ 1.136 CH₂CH₃2-fluorophenyl H CH₃ 1.137 CH₂CH₃ 2-chlorophenyl H CH₃ 1.138 CH₂CH₃2-trifluoromethylphenyl H CH₃ 1.139 CH₂CH₃ 2-nitrophenyl H CH₃ 1.140CH₂CH₃ 2-methylphenyl H CH₃ 1.141 CH₂CH₃ 2-methylsulfonylphenyl H CH₃1.142 CH₂CH₃ 2-cyanophenyl H CH₃ 1.143 CH₂CH₃ 3-fluorophenyl H CH₃ 1.144CH₂CH₃ 3-chlorophenyl H CH₃ 1.145 CH₂CH₃ 3-trifluoromethylphenyl H CH₃1.146 CH₂CH₃ 3-nitrophenyl H CH₃ 1.147 CH₂CH₃ 3-methylphenyl H CH₃ 1.148CH₂CH₃ 3-methylsulfonylphenyl H CH₃ 1.149 CH₂CH₃ 3-cyanophenyl H CH₃1.150 CH₂CH₃ 4-fluorophenyl H CH₃ 1.151 CH₂CH₃ 4-chlorophenyl H CH₃1.152 CH₂CH₃ 4-trifluoromethylphenyl H CH₃ 1.153 CH₂CH₃ 4-nitrophenyl HCH₃ 1.154 CH₂CH₃ 4-methylphenyl H CH₃ 1.155 CH₂CH₃4-methylsulfonylphenyl H CH₃ 1.156 CH₂CH₃ 4-cyanophenyl H CH₃ 1.157CH₂CH₃ H phenyl H 1.158 CH₂CH₃ H 2-fluorophenyl H 1.159 CH₂CH₃ H2-chlorophenyl H 1.160 CH₂CH₃ H 2-trifluoromethylphenyl H 1.161 CH₂CH₃ H2-nitrophenyl H 1.162 CH₂CH₃ H 2-methylphenyl H 1.163 CH₂CH₃ H2-methylsulfonylphenyl H 1.164 CH₂CH₃ H 2-cyanophenyl H 1.165 CH₂CH₃ H3-fluorophenyl H 1.166 CH₂CH₃ H 3-chlorophenyl H 1.167 CH₂CH₃ H3-trifluoromethylphenyl H 1.168 CH₂CH₃ H 3-nitrophenyl H 1.169 CH₂CH₃ H3-methylphenyl H 1.170 CH₂CH₃ H 3-methylsulfonylphenyl H 1.1.71 CH₂CH₃ H3-cyanophenyl H 1.172 CH₂CH₃ H 4-fluorophenyl H 1.173 CH₂CH₃ H4-chlorophenyl H 1.174 CH₂CH₃ H 4-trifluoromethylphenyl H 1.175 CH₂CH₃ H4-nitrophenyl H 1.176 CH₂CH₃ H 4-methylphenyl H 1.177 CH₂CH₃ H4-methylsulfonylphenyl H 1.178 CH₂CH₃ H 4-cyanophenyl H 1.179 CH₂CH₃ CH₃H CH₂CH₃ 1.180 CH₂CH₃ CH₂CH₃ H CH₂CH₃ 1.181 CH₂CH₃ Cl H CH₂CH₃ 1.182CH₂CH₃ Br H CH₂CH₃ 1.183 CH₂CH₃ NO₂ H CH₂CH₃ 1.184 CH₂CH₃ CH₃O H CH₂CH₃1.185 CH₂CH₃ CH₃S H CH₂CH₃ 1.186 CH₂CH₃ CH₃SO₂ H CH₂CH₃ 1.187 CH₂CH₃CH₂═CH H CH₂CH₃ 1.188 CH₂CH₃ —C•CH H CH₂CH₃ 1.189 CH₂CH₃ phenyl H CH₂CH₃1.190 CH₂CH₃ 2-fluorophenyl H CH₂CH₃ 1.191 CH₂CH₃ 2-chlorophenyl HCH₂CH₃ 1.192 CH₂CH₃ 2-trifluoromethylphenyl H CH₂CH₃ 1.193 CH₂CH₃2-nitrophenyl H CH₂CH₃ 1.194 CH₂CH₃ 2-methylphenyl H CH₂CH₃ 1.195 CH₂CH₃2-methylsulfonylphenyl H CH₂CH₃ 1.196 CH₂CH₃ 2-cyanophenyl H CH₂CH₃1.197 CH₂CH₃ 3-fluorophenyl H CH₂CH₃ 1.198 CH₂CH₃ 3-chlorophenyl HCH₂CH₃ 1.199 CH₂CH₃ 3-trifluoromethylphenyl H CH₂CH₃ 1.200 CH₂CH₃3-nitrophenyl H CH₂CH₃ 1.201 CH₂CH₃ 3-methylphenyl H CH₂CH₃ 1.202 CH₂CH₃3-methylsulfonylphenyl H CH₂CH₃ 1.203 CH₂CH₃ 3-cyanophenyl H CH₂CH₃1.204 CH₂CH₃ 4-fluorophenyl H CH₂CH₃ 1.205 CH₂CH₃ 4-chlorophenyl HCH₂CH₃ 1.206 CH₂CH₃ 4-trifluoromethylphenyl H CH₂CH₃ 1.207 CH₂CH₃4-nitrophenyl H CH₂CH₃ 1.208 CH₂CH₃ 4-methylphenyl H CH₂CH₃ 1.209 CH₂CH₃4-methylsulfonylphenyl H CH₂CH₃ 1.210 CH₂CH₃ 4-cyanophenyl H CH₂CH₃1.211 OCH₃ H phenyl H 1.212 OCH₃ H 2-fluorophenyl H 1.213 OCH₃ H2-chlorophenyl H 1.214 OCH₃ H 2-trifluoromethylphenyl H 1.215 OCH₃ H2-nitrophenyl H 1.216 OCH₃ H 2-methylphenyl H 1.217 OCH₃ H2-methylsulfonylphenyl H 1.218 OCH₃ H 2-cyanophenyl H 1.219 OCH₃ H3-fluorophenyl H 1.220 OCH₃ H 3-chlorophenyl H 1.221 OCH₃ H3-trifluoromethylphenyl H 1.222 OCH₃ H 3-nitrophenyl H 1.223 OCH₃ H3-methylphenyl H 1.224 OCH₃ H 3-methylsulfonylphenyl H 1.225 OCH₃ H3-cyanophenyl H 1.226 OCH₃ H 4-fluorophenyl H 1.227 OCH₃ H4-chlorophenyl H 1.228 OCH₃ H 4-trifluoromethylphenyl H 1.229 OCH₃ H4-nitrophenyl H 1.230 OCH₃ H 4-methylphenyl H 1.231 OCH₃ H4-methylsulfonylphenyl H 1.232 OCH₃ H 4-cyanophenyl H

Table 2 covers 232 compounds of the following type

where G, R⁵ and R⁶ are hydrogen, R⁷ is methyl and R¹, R², R³ and R⁴ areas described in Table 1.

Table 3 covers 232 compounds of the following type

where G and R⁵ are hydrogen, R⁶ and R⁷ are methyl and R¹, R², R³ and R⁴are as described in Table 1.

Table 4 covers 232 compounds of the following type

where G, R⁵, R⁶ and R⁷ are all hydrogen, and R¹, R², R³ and R⁴ are asdescribed in Table 1.

Table 5 covers 232 compounds of the following type

where G, R⁵ and R⁶ are hydrogen, R⁷ is methyl and R¹, R², R³ and R⁴ areas described in Table 1.

Table 6 covers 232 compounds of the following type

where G and R⁵ are hydrogen, R⁶ and R⁷ are methyl and R¹, R², R³ and R⁴are as described in Table 1.

Table 7 covers 232 compounds of the following type

where G, R⁵R⁶ and R⁷ are all hydrogen, and R¹, R², R³ and R⁴ are asdescribed in Table 1.

Table 8 covers 232 compounds of the following type

where G, R⁵ and R⁶ are hydrogen, R⁷ is methyl and R¹, R², R³ and R⁴ areas described in Table 1.

Table 9 covers 232 compounds of the following type

where G and R⁵ are hydrogen, R⁶ and R⁷ are methyl and R¹, R², R³ and R⁴are as described in Table 1

Table 10 covers 232 compounds of the following type

where G, R⁵, R⁶ and R⁷ are all hydrogen, and R¹, R², R³ and R⁴ are asdescribed in Table 1.

Table 11 covers 232 compounds of the following type

where G, R⁵ and R⁶ are hydrogen, R⁷ is methyl and R¹, R², R³ and R⁴ areas described in Table 1.

Table 12 covers 232 compounds of the following type

where G and R⁵ are hydrogen, R⁶ and R⁷ are methyl and R¹, R², R³ and R⁴are as described in Table 1.

Table 13 covers 232 compounds of the following type

where G, R⁵, R⁶ and R⁷ are all hydrogen, and R¹, R², R³ and R⁴ are asdescribed in Table 1.

Table 14 covers 232 compounds of the following type

where G, R⁵ and R⁶ are hydrogen, R⁷ is methyl and R¹, R², R³ and R⁴ areas described in Table 1.

Table 15 covers 232 compounds of the following type

where G and R⁵ are hydrogen, R⁶ and R⁷ are methyl and R¹, R², R³ and R⁴are as described in Table 1.

Table 16 covers 232 compounds of the following type

where G, R⁵, R⁶ and R⁷ are all hydrogen, and R¹, R², R³ and R⁴ are asdescribed in Table 1.

Table 17 covers 232 compounds of the following type

where G, R⁵ and R⁶ are hydrogen, R⁷ is methyl and R¹, R², R³ and R⁴ areas described in Table 1.

Table 18 covers 232 compounds of the following type

where G and R⁵ are hydrogen, R⁶ and R⁷ are methyl and R¹, R², R³ and R⁴are as described in Table 1

Table 19 covers 232 compounds of the following type

where G, R⁵, R⁶ and R⁷ are all hydrogen, and R¹, R², R³ and R⁴ are asdescribed in Table 1.

Table 20 covers 232 compounds of the following type

where G, R⁵ and R⁶ are hydrogen, R⁷ is methyl and R¹, R², R³ and R⁴ areas described in Table 1.

Table 21 covers 232 compounds of the following type

where G and R⁵ are hydrogen, R⁶ and R⁷ are methyl and R¹, R², R³ and R⁴are as described in Table 1.

Table 22 covers 232 compounds of the following type

where G, R⁵, R⁶ and R⁷ are all hydrogen, and R¹, R², R³ and R⁴ are asdescribed in Table 1.

Table 23 covers 232 compounds of the following type

where G, R⁵ and R⁶ are hydrogen, R⁷ is methyl and R¹, R², R³ and R⁴ areas described in Table 1

Table 24 covers 232 compounds of the following type

where G, R⁵, R⁶ and R⁷ are all hydrogen, and R¹, R², R³ and R⁴ are asdescribed in Table 1.

Table 25 covers 232 compounds of the following type

where G, R⁵ and R⁶ are hydrogen, R⁷ is methyl and R¹, R², R³ and R⁴ areas described in Table 1.

Table 26 covers 232 compounds of the following type

where G, R⁵, R⁶ and R⁷ are all hydrogen, and R¹, R², R³ and R⁴ are asdescribed in Table 1.

Table 27 covers 232 compounds of the following type

where G, R⁵ and R⁶ are hydrogen, R⁷ is methyl and R¹, R², R³ and R⁴ areas described in Table 1.

Table 28 covers 232 compounds of the following type

where G and R⁵ are hydrogen, R⁶ and R⁷ are methyl and R¹, R², R³ and R⁴are as described in Table 1.

Table 29 covers 232 compounds of the following type

where G, R⁵, R⁶ and R⁷ are all hydrogen, and R¹, R², R³ and R⁴ are asdescribed in Table 1.

Table 30 covers 232 compounds of the following type

where G, R⁵ and R⁶ are hydrogen, R⁷ is methyl and R¹, R², R³ and R⁴ areas described in Table 1.

Table 31 covers 232 compounds of the following type

where G, R⁵, R⁶ and R⁷ are all hydrogen, and R¹, R², R³ and R⁴ are asdescribed in Table 1.

Table 32 covers 232 compounds of the following type

where G, R⁵, R⁶and R⁷ are all hydrogen, and R¹, R², R³and R⁴ are asdescribed in Table 1.

Table 33 covers 232 compounds of the following type

where G, R⁵, R⁶ and R⁷ are all hydrogen, and R¹, R², R³ and R⁴ are asdescribed in Table 1.

Table 34 covers 232 compounds of the following type

where G, R⁵, R⁶ and R⁷ are all hydrogen, and R¹, R², R³ and R⁴ are asdescribed in Table 1.

Table 35 covers 232 compounds of the following type

where G, R⁵, R⁶ and R⁷ are all hydrogen, and R¹, R², R³ and R⁴ are asdescribed in Table 1.

Table 36 covers 232 compounds of the following type

where G, R⁵, R⁶ and R⁷ are all hydrogen, and R¹, R², R³ and R⁴ are asdescribed in Table 1.

Table 37 covers 232 compounds of the following type

where G, R⁵, R⁶ and R⁷ are all hydrogen, and R¹, R², R³ and R⁴ are asdescribed in Table 1.

Table 38 covers 232 compounds of the following type

where G, R⁵ and R⁶ are hydrogen, R⁷ is methyl and R¹, R², R³ and R⁴ areas described in Table 1.

Table 39 covers 232 compounds of the following type

where G and R⁵ are hydrogen, R⁶ and R⁷ are methyl and R¹, R², R³ and R⁴are as described in Table 1.

Table 40 covers 232 compounds of the following type

where G, R⁵, R⁶ and R⁷ are all hydrogen, and R¹, R², R³ and R⁴ are asdescribed in Table 1.

Table 41 covers 232 compounds of the following type

where G, R⁵ and R⁶ are hydrogen, R⁷ is methyl and R¹, R², R³ and R⁴ areas described in Table 1.

Table 42 covers 232 compounds of the following type

where G and R⁵ are hydrogen, R⁶ and R⁷ are methyl and R¹, R², R³ and R⁴are as described in Table 1.

Table 43 covers 232 compounds of the following type

where G, R⁵, R⁶ and R⁷ are all hydrogen, and R¹, R², R³ and R⁴ are asdescribed in Table 1.

Table 44 covers 232 compounds of the following type

where G, R⁵ and R⁶ are hydrogen, R⁷ is methyl and R¹, R², R³ and R⁴ areas described in Table 1.

Table 45 covers 232 compounds of the following type

where G and R⁵ are hydrogen, R⁶ and R⁷ are methyl and R¹, R², R³ and R⁴are as described in Table 1.

Table 46 covers 232 compounds of the following type

where G, R⁵, R⁶ and R⁷ are all hydrogen, and R¹, R², R³ and R⁴ are asdescribed in Table 1.

Table 47 covers 232 compounds of the following type

where G, R⁵ and R⁶ are hydrogen, R⁷ is methyl and R¹, R², R³ and R⁴ areas described in Table 1.

Table 48 covers 232 compounds of the following type

where G and R⁵ are hydrogen, R⁶ and R⁷ are methyl and R¹, R², R³ and R⁴are as described in Table 1.

Table 49 covers 232 compounds of the following type

where G, R⁵, R⁶ and R⁷ are all hydrogen, and R¹, R², R³ and R⁴ are asdescribed in Table 1.

Table 50 covers 232 compounds of the following type

where G, R⁵ and R⁶ are hydrogen, R⁷ is methyl and R¹, R², R³ and R⁴ areas described in Table 1.

Table 51 covers 232 compounds of the following type

where G and R⁵ are hydrogen, R⁶ and R⁷ are methyl and R¹, R², R³ and R⁴are as described in Table 1.

Table 52 covers 232 compounds of the following type

where G, R⁵, R⁶ and R⁷ are all hydrogen, and R¹, R², R³ and R⁴ are asdescribed in Table 1.

Table 53 covers 232 compounds of the following type

where G, R⁵ and R⁶ are hydrogen, R⁷ is methyl and R¹, R², R³ and R⁴ areas described in Table 1.

Table 54 covers 232 compounds of the following type

where G and R⁵ are hydrogen, R⁶ and R⁷ are methyl and R¹, R², R³ and R⁴are as described in Table 1.

Table 55 covers 232 compounds of the following type

where G, R⁵, R⁶ and R⁷ are all hydrogen, and R¹, R², R³ and R⁴ are asdescribed in Table 1.

Table 56 covers 232 compounds of the following type

where G, R⁵ and R⁶ are hydrogen, R⁷ is methyl and R¹, R², R³ and R⁴ areas described in Table 1.

Table 57 covers 232 compounds of the following type

where G and R⁵ are hydrogen, R⁶ and R⁷ are methyl and R¹, R², R³ and R⁴are as described in Table 1.

Table 58 covers 232 compounds of the following type

where G, R⁵, R⁶ and R⁷ are all hydrogen, and R¹, R², R³ and R⁴ are asdescribed in Table 1.

Table 59 covers 232 compounds of the following type

where G, R⁵ and R⁶ are hydrogen, R⁷ is methyl and R¹, R², R³ and R⁴ areas described in Table 1.

Table 60 covers 232 compounds of the following type

where G and R⁵ are hydrogen, R⁶ and R⁷ are methyl and R¹, R², R³ and R⁴are as described in Table 1.

Table 61 covers 232 compounds of the following type

where G, R⁵, R⁶ and R⁷ are all hydrogen, and R¹, R², R³ and R⁴ are asdescribed in Table 1.

Table 62 covers 232 compounds of the following type

where G, R⁵ and R⁶ are hydrogen, R⁷ is methyl and R¹, R², R³ and R⁴ areas described in Table 1.

Table 63 covers 232 compounds of the following type

where G and R⁵ are hydrogen, R⁶ and R⁷ are methyl and R¹, R², R³ and R⁴are as described in Table 1.

Table 64 covers 232 compounds of the following type

where G, R⁵, R⁶ and R⁷ are all hydrogen, and R¹, R², R³ and R⁴ are asdescribed in Table 1.

Table 65 covers 232 compounds of the following type

where G, R⁵ and R⁶ are hydrogen, R⁷ is methyl and R¹, R², R³ and R⁴ areas described in Table 1.

Table 66 covers 232 compounds of the following type

where G and R⁵ are hydrogen, R⁶ and R⁷ are methyl and R¹, R², R³ and R⁴are as described in Table 1.

Table 67 covers 232 compounds of the following type

where G, R⁵, R⁶ and R⁷ are all hydrogen, and R¹, R², R³ and R⁴ are asdescribed in Table 1.

Table 68 covers 232 compounds of the following type

where G, R⁵ and R⁶ are hydrogen, R⁷ is methyl and R¹, R², R³ and R⁴ areas described in Table 1.

Table 69 covers 232 compounds of the following type

where G and R⁵ are hydrogen, R⁶ and R⁷ are methyl and R¹, R², R³ and R⁴are as described in Table 1.

Table 70 covers 232 compounds of the following type

where G, R⁵, R⁶ and R⁷ are all hydrogen, and R¹, R², R³ and R⁴ are asdescribed in Table 1.

Table 71 covers 232 compounds of the following type

where G, R⁵ and R⁶ are hydrogen, R⁷ is methyl and R¹, R², R³ and R⁴ areas described in Table 1.

Table 72 covers 232 compounds of the following type

where G and R⁵ are hydrogen, R⁶ and R⁷ are methyl and R¹, R², R³ and R⁴are as described in Table 1.

Table 73 covers 232 compounds of the following type

where G, R⁵, R⁶ and R⁷ are all hydrogen, and R¹, R², R³ and R⁴ are asdescribed in Table 1.

Table 74 covers 232 compounds of the following type

where G, R⁵ and R⁶ are hydrogen, R⁷ is methyl and R¹, R², R³ and R⁴ areas described in Table 1.

Table 75 covers 232 compounds of the following type

where G and R⁵ are hydrogen, R⁶ and R⁷ are methyl and R¹, R², R³ and R⁴are as described in Table 1.

Table 76 covers 232 compounds of the following type

where G, R⁵, R⁶ and R⁷ are all hydrogen, and R¹, R², R³ and R⁴ are asdescribed in Table 1.

Table 77 covers 232 compounds of the following type

where G, R⁵ and R⁶ are hydrogen, R⁷ is methyl and R¹, R², R³ and R⁴ areas described in Table 1.

Table 78 covers 232 compounds of the following type

where G and R⁵ are hydrogen, R⁶ and R⁷ are methyl and R¹, R², R³ and R⁴are as described in Table 1.

Table 79 covers 232 compounds of the following type

where G, R⁵, R⁶ and R⁷ are all hydrogen, and R¹, R², R³ and R⁴ are asdescribed in Table 1.

Table 80 covers 232 compounds of the following type

where G, R⁵ and R⁶ are hydrogen, R⁷ is methyl and R¹, R², R³ and R⁴ areas described in Table 1.

Table 81 covers 232 compounds of the following type

where G and R⁵ are hydrogen, R⁶ and R⁷ are methyl and R¹, R², R³ and R⁴are as described in Table 1.

Biological Examples Example A

Seeds of a variety of test species were sown in standard soil in pots.After cultivation for one day (pre-emergence) or after 10 dayscultivation (post-emergence) under controlled conditions in aglasshouse, the plants were sprayed with an aqueous spray solutionderived from the formulation of the technical active ingredient in 0.6ml acetone and 45 ml formulation solution containing 10.6% Emulsogen EL(Registry number 61791-12-6), 42.2% N-methylpyrrolidone, 42.2%dipropylene glycol monomethyl ether (Registry number 34590-94-8) and0.2% X-77 (Registry number 11097-66-8). The test plants were then grownin a greenhouse under optimum conditions until, 15 days later forpost-emergence and 20 days for pre-emergence, the test was evaluated(100=total damage to plant; 0=no damage to plant).

Test Plants:

Alopecurus myosuroides (ALOMY), Avena fatua (AVEFA), Lolium perenne(LOLPE), Setaria faberi (SETFA), Digitaria sanguinalis (DIGSA),Echinochloa crus-galli (ECHCG)

Pre-Emergence Activity

Compound Rate Number g/ha ALOMY AVEFA LOLPE SETFA DIGSA ECHCG A-1 500 7040 80 90 100 50 A-2 500 20 40 10 60 50 100 A-3 500 80 90 100 100 100 100A-4 500 60 40 30 80 70 100 A-5 500 100 100 100 100 100 100 A-6 500 90 6070 80 100 100 A-7 500 100 100 100 80 100 100 A-8 500 100 50 100 70 10070 A-9 500 100 60 100 90 100 70 A-10 500 50 50 70 60 60 80 A-11 500 100100 100 — — 70 A-12 500 — 40 100 60 70 70 A-13 500 30 20 10 30 30 30A-14 500 80 70 90 100 100 80 A-15 500 10 40 0 20 20 10 A-16 500 100 90100 — 100 100 A-17 500 100 100 100 100 100 100 A-18 500 90 100 100 100100 100 A-19 500 100 60 100 100 100 100 A-20 500 50 10 40 70 40 100 A-31500 60 50 40 100 100 70 B-1 500 90 50 90 80 100 100Post Emergency Activity

Compound Rate Number g/ha ALOMY AVEFA LOLPE SETFA DIGSA ECHCG A-1 500 7080 70 100 100 90 A-2 500 70 40 50 90 90 100 A-3 500 80 80 80 80 100 100A-4 500 80 70 70 100 100 100 A-5 500 90 90 90 100 90 100 A-6 500 80 10080 80 90 100 A-7 500 90 100 90 80 80 100 A-8 500 60 50 80 70 70 100 A-9500 80 70 80 80 70 90 A-10 500 80 80 60 50 70 50 A-11 500 100 90 90 8090 100 A-12 500 80 80 80 70 70 80 A-13 500 80 30 70 50 90 100 A-14 500100 100 90 100 70 100 A-15 500 60 30 30 30 70 50 A-16 500 60 90 90 80100 70 A-17 125 90 100 90 50 80 100 A-18 125 100 90 100 50 80 100 A-19125 70 20 70 60 60 70 A-20 125 40 60 40 80 100 100 A-31 125 60 60 60 4030 50 B-1 500 50 0 60 80 90 70

Example B

Seeds of a variety of test species were sown in standard soil in pots.After cultivation for one day (pre-emergence) or after 8 dayscultivation (post-emergence) under controlled conditions in a glasshouse(at 24/16° C., day/night; 14 hours light; 65% humidity), the plants weresprayed with an aqueous spray solution derived from the formulation ofthe technical active ingredient in acetone/water (50:50) solutioncontaining 0.5% Tween 20 (polyoxyethelyene sorbitan monolaurate, CAS RN9005-64-5). The test plants were then grown in a glasshouse undercontrolled conditions in a glasshouse (at 24/16° C., day/night; 14 hourslight; 65% humidity) and watered twice daily. After 13 days for pre andpost-emergence, the test was evaluated (100=total damage to plant; 0=nodamage to plant).

Test Plants:

Alopecurus myosuroides (ALOMY), Avena fatua (AVEFA), Setaria faberi(SETFA), Echinochloa crus-galli (ECHCG), Solanum nigrum (SOLNI) andAmaranthus retroflexus (AMARE)

Pre-Emergence Activity

Compound Rate Number g/ha SOLNI AMARE SETFA ALOMY ECHCG AVEFA A-27 10000 0 0 0 0 0 A-29 1000 30 50 0 20 20 0 A-31 1000 0 0 100 100 100 40 A-331000 0 0 100 50 90 60 A-34 1000 0 0 90 50 100 60 A-36 1000 0 0 100 60 9040 A-37 1000 20 20 100 80 100 90 A-38 1000 0 0 100 30 100 20 A-39 1000 00 0 0 0 0 A-40 1000 0 0 0 0 30 0 A-41 1000 0 0 100 90 100 80 A-45 1000100 0 90 60 100 70 A-46 1000 0 0 90 20 40 40 A-48 1000 0 0 20 0 20 0A-53 1000 0 0 0 0 0 0 A-54 1000 0 0 0 60 0 10 A-55 1000 0 0 60 0 60 20A-56 1000 0 0 70 20 0 0 A-57 1000 0 0 90 40 0 0 A-58 1000 0 0 30 20 60 0A-59 1000 0 0 60 20 0 0 A-60 1000 0 0 30 0 30 0 A-61 1000 0 0 30 0 20 0A-62 1000 0 0 60 20 50 0 A-63 1000 0 20 70 0 20 0 A-64 1000 0 0 50 0 500 A-65 1000 20 30 60 20 70 0Post-Emergence Activity

Compound Rate Number g/ha SOLNI AMARE SETFA ALOMY ECHCG AVEFA A-27 10000 0 60 10 30 0 A-29 1000 20 70 60 10 60 0 A-31 1000 0 0 100 100 100 90A-33 1000 70 60 80 30 100 70 A-34 1000 0 20 90 50 100 100 A-36 1000 50 0100 70 100 70 A-37 1000 70 40 100 90 100 100 A-38 1000 20 0 100 30 90 40A-39 1000 0 0 90 60 80 80 A-40 1000 0 30 90 70 100 70 A-41 1000 40 40100 90 100 70 A-45 1000 10 0 100 100 100 100 A-46 1000 20 20 90 90 10080 A-48 1000 0 10 80 60 80 60 A-53 1000 0 0 60 50 70 50 A-54 1000 0 0 00 70 0 A-55 1000 0 0 100 90 100 90 A-56 1000 0 0 90 80 100 0 A-57 1000 00 90 70 90 20 A-58 1000 0 0 90 60 90 40 A-59 1000 0 0 90 70 90 20 A-601000 0 0 90 60 90 10 A-61 1000 0 0 100 90 100 80 A-62 1000 0 0 100 90100 80 A-63 1000 0 0 100 90 100 90 A-64 1000 0 0 100 80 100 80 A-65 100060 90 70 40 70 20

What is claimed is:
 1. A compound of formula I

wherein R¹ is methyl, ethyl, n-propyl, isopropyl, cyclopropyl,halomethyl, haloethyl, halogen, vinyl, ethynyl, methoxy, ethoxy,halomethoxy or haloethoxy; R² and R³ are, independently hydrogen,halogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy,C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₃-C₆alkenyloxy,C₃-C₆haloalkenyloxy, C₃-C₆alkynyloxy, C₃-C₆cycloalkyl, C₁-C₆alkylthio,C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆alkoxysulfonyl,C₁-C₆haloalkoxysulfonyl, cyano, nitro; phenyl, phenyl substituted byC₁-C₄alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃alkoxy-C₁-C₃alkoxy,C₁-C₃haloalkoxy, aminocarbonyl, cyano, nitro, halogen, C₁-C₃alkylthio,C₁-C₃alkylsulfinyl or C₁-C₃alkylsulfonyl; or phenyl wherein 2 adjacentcarbon atoms are bridged by a —O—CH₂—O— or —O—CH₂—CH₂—O— group; orheteroaryl or heteroaryl substituted by C₁-C₄alkyl, C₁-C₃haloalkyl,C₁-C₃alkoxy, cyclopropyl-C₁-C₃alkoxy, C₁-C₃haloalkoxy, cyano, nitro,halogen, C₁-C₃alkylthio, C₁-C₃alkylsulfinyl or C₁-C₃alkylsulfonyl; R⁴ ishydrogen, methyl, ethyl, n-propyl, isopropyl, halomethyl, haloethyl,halogen, vinyl, ethynyl, methoxy, ethoxy, halomethoxy or haloethoxy; R⁵is hydrogen or methyl; R⁶ and R⁷ are independently hydrogen, methyl,ethyl, C₃-C₆cycloalkyl, halogen, halomethyl, haloethyl, halogen,methoxy, halomethoxy, haloethoxy, or together R⁶ and R⁷ are joined toform together with the carbon atom to which they are attached a 3-7membered ring or a 3-7 membered ring substituted by one or two methylgroups; and Q is a 3- to 8-membered saturated or mono-unsaturatedheterocycle containing at least one heteroatom selected from O, N andS(O)_(p); or Q is a 3- to 8-membered saturated or mono-unsaturatedheterocycle containing at least one heteroatom selected from O, N andS(O)_(p), which is substituted by ═O, C₁-C₄alkyl, C₁-C₄haloalkyl,C₁-C₄alkoxy-C₁-C₂alkyl, C₃-C₆cycloalkyl or C₃-C₆cycloalkyl-C₁-C₃alkyl,or is substituted by a 3- to 6-membered heterocyclyl containing at leastone heteroatom selected from O and N, or is substituted by a 3- to6-membered heterocyclyl-C₁-C₃alkyl containing at least one heteroatomselected from O and N, or is substituted by a spiro-C₃-C₆cycloalkyl or aspiro-3- to 8-membered saturated heterocycle containing at least oneheteroatom selected from O, N and S(O)_(p), or is bridged by a —O—CH₂—group; or Q is a 6- to 10-membered bicyclic heterocycle containing atleast one heteroatom selected from O, N and S(O)_(p); and p is 0, 1 or2; and G is hydrogen, C₃alkenyl, C₃alkynyl, an alkali metal, alkalineearth metal, a sulfonium, an ammonium or a latentiating group; wherein,when G is a latentiating group, then G is selected from the groups—C(X¹)—R⁶, —C(X²)—X³—R⁷, —C(X⁴)—NR⁸R⁹, —SO₂R¹⁰, P(X⁵)R¹¹R¹² andCH₂—X⁶—R¹³; wherein X¹, X², X³, X⁴, X⁵ and X⁶ are independently of eachother oxygen or sulfur; R⁶, R⁷, R⁸ and R⁹ are each independently of eachother hydrogen, C₁-C₁₀alkyl, C₂-C₁₀alkenyl, C₂-C₁₀alkynyl,C₁-C₁₀haloalkyl, C₁-C₁₀cyanoalkyl, C₁-C₁₀-nitroalkyl, C₁-C₁₀aminoalkyl,C₁-C₅aminoalkylC₁-C₅alkyl, C₂-C₈dialkylaminoC₁-C₅alkyl,C₃-C₇cycloalkylC₁-C₅alkyl, C₂-C₁₀alkoxyalkyl, C₄-C₁₀alkenyloxyalkyl,C₄-C₁₀alkynyloxyalkyl, C₂-C₁₀alkylthioalkyl,C₁-C₅alkylsulfinylC₁-C₅alkyl, C₁-C₅alkylsulfonylC₁-C₅alkyl,C₂-C₈alkylideneaminooxyC₁-C₅alkyl, C₁-C₅alkylcarbonylC₁-C₅alkyl,C₁-C₅alkoxycarbonylC₁-C₅alkyl, C₁-C₅alkylaminocarbonylC₁-C₅alkyl,C₂-C₈dialkylaminocarbonylC₁-C₅alkyl, C₁-C₅alkylcarbonylaminoC₁-C₅alkyl,N—C₁-C₅alkylcarbonyl-N—C₂-C₅alkylaminoalkyl,C₃-C₆trialkylsilylC₁-C₅alkyl, phenylC₁-C₅alkyl, heteroarylC₁-C₅alkyl,C₂-C₅alkenyl, C₂-C₅haloalkenyl, C₃-C₈cycloalkyl; phenyl or phenylsubstituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy,halogen, cyano or nitro; or heteroaryl or heteroarylamino substituted byC₁-C₃ alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen,cyano or nitro; diheteroarylamino or diheteroarylamino substituted byC₁-C₃ alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen,cyano or nitro; phenylamino or phenylamino substituted by C₁-C₃alkyl,C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or bynitro; diphenylamino or diphenylamino substituted by C₁-C₃alkyl,C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or bynitro; or C₃-C₇cycloalkylamino, di-C₃-C₇cycloalkylamino orC₃-C₇cycloalkoxy; R¹⁰, R¹¹, R¹² are hydrogen, C₁-C₁₀alkyl,C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₁-C₁₀haloalkyl, C₁-C₁₀cyanoalkyl,C₁-C₁₀nitroalkyl, C₁-C₁₀aminoalkyl, C₁-C₅aminoalkylC₁-C₅alkyl,C₂-C₈dialkylaminoC₁-C₅alkyl, C₃-C₇cycloalkylC₁-C₅alkyl,C₂-C₁₀alkoxyalkyl, C₄-C₁₀alkenyloxyalkyl, C₄-C₁₀alkynyloxyalkyl,C₂-C₁₀alkylthioalkyl, C₁-C₅alkylsulfinylC₁-C₅alkyl,C₁-C₅alkylsulfonylC₁-C₅alkyl, C₂-C₈alkylideneaminooxyC₁-C₅alkyl,C₁-C₅alkylcarbonylC₁-C₅alkyl, C₁-C₅alkoxycarbonylC₁-C₅alkyl,C₁-C₅aminocarbonylC₁-C₅alkyl, C₂-C₈dialkylaminocarbonylC₁-C₅alkyl,C₁-C₅alkylcarbonylaminoC₁-C₅alkyl,N—C₁-C₅alkylcarbonyl-N—C₂-C₅alkylaminoalkyl,C₃-C₆trialkylsilylC₁-C₅alkyl, phenylC₁-C₅alkyl, heteroarylC₁-C₅alkyl,C₂-C₅alkenyl, C₂-C₅haloalkenyl, C₃-C₈cycloalkyl; phenyl or phenylsubstituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy,halogen, cyano or nitro; heteroaryl or heteroarylamino substituted byC₁-C₃ alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen,cyano or by nitro; diheteroarylamino or diheteroarylamino substituted byC₁-C₃ alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen,cyano or nitro; phenylamino or phenylamino substituted by C₁-C₃alkyl,C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or nitro;diphenylamino or diphenylamino substituted by C₁-C₃alkyl,C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano or nitro;or C₃-C₇cycloalkylamino, diC₃-C₇cycloalkylamino, C₃-C₇cycloalkoxy,C₁-C₁₀alkoxy, C₁-C₁₀haloalkoxy, C₁-C₅alkylamino, C₂-C₈dialkylamino; orbenzyloxy or phenoxy, wherein the benzyl and phenyl groups may in turnbe substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,C₁-C₃haloalkoxy, halogen, cyano or nitro; and R¹³ is C₁-C₁₀alkyl,C₂-C₁₀alkenyl, C₂-C₁₀alkynyl, C₁-C₁₀haloalkyl, C₁-C₁₀cyanoalkyl,C₁-C₁₀nitroalkyl, C₁-C₁₀aminoalkyl, C₁-C₅aminoalkylC₁-C₅alkyl,C₂-C₈dialkylaminoC₁-C₅alkyl, C₃-C₇cycloalkylC₁-C₅alkyl,C₂-C₁₀alkoxyalkyl, C₄-C₁₀alkenyloxyalkyl, C₄-C₁₀alkynyloxyalkyl,C₁-C₁₀alkylthioalkyl, C₁-C₅alkylsulfinylC₁-C₅alkyl,C₁-C₅alkylsulfonylC₁-C₅alkyl, C₂-C₈alkylideneaminooxyC₁-C₅alkyl,C₁-C₅alkylcarbonylC₁-C₅alkyl, C₁-C₅alkoxycarbonylC₁-C₅alkyl,C₁-C₅aminocarbonylC₁-C₅alkyl, C₂-C₈dialkylaminocarbonylC₁-C₅alkyl,C₁-C₅alkylcarbonylaminoC₁-C₅alkyl,N—C₁-C₅alkylcarbonyl-N—C₂-C₅alkylaminoalkyl,C₃-C₆trialkylsilylC₁-C₅alkyl, phenylC₁-C₅alkyl, heteroarylC₁-C₅alkyl,phenoxyC₁-C₅alkyl, heteroaryloxyC₁-C₅alkyl, C₂-C₅alkenyl,C₂-C₅haloalkenyl, C₃-C₈cycloalkyl; phenyl or phenyl substituted byC₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen or bynitro; heteroaryl or heteroarylamino, or heteroaryl or heteroarylaminosubstituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy,halogen, cyano or by nitro; diheteroarylamino or diheteroarylaminosubstituted by C₁-C₃ alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,C₁-C₃haloalkoxy, halogen, cyano or by nitro; phenylamino or phenylaminosubstituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy,halogen, cyano or by nitro; diphenylamino or diphenylamino substitutedby C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen,cyano or by nitro; or C₃-C₇cycloalkylamino, diC₃-C₇cycloalkylamino,C₃-C₇cycloalkoxy or C₁-C₁₀alkylcarbonyl; and wherein “heteroaryl” meansthienyl, furyl, pyrrolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl,pyrazolyl, imidazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl,pyrazinyl, triazinyl, oxadiazolyl or thiadiazolyl, or, whereappropriate, an N-oxide or a salt thereof.
 2. A compound according toclaim 1, wherein R¹ is methyl, ethyl, cyclopropyl or methoxy.
 3. Acompound according to claim 1, wherein R² and R³ are independentlyhydrogen, halogen, C₁-C₆alkyl, C₁-C₆alkoxy, C₂-C₆alkenyl, C₂-C₆alkynyl,phenyl or phenyl substituted by C₁-C₄alkyl, C₁-C₃haloalkyl, cyano,nitro, halogen or C₁-C₃alkylsulfonyl.
 4. A compound according to claim1, wherein R⁴ is hydrogen, methyl, ethyl, chlorine, bromine, vinyl,ethynyl or methoxy.
 5. A compound according to claim 1, wherein R⁵ ishydrogen.
 6. A compound according to claim 1, wherein one of R⁶ and R⁷is hydrogen or both of R⁶ and R⁷ are hydrogen.
 7. A compound accordingto claim 1, wherein G is hydrogen, an alkali metal or alkaline earthmetal.
 8. A compound according to claim 1, wherein Q is a group of theformula

wherein R is C₁₋₄ alkyl, C₁₋₄ haloalkyl, C₁₋₄ alkoxyC₁₋₂ alkyl or C₃₋₆cycloalkyl, n is 0 to 4, and -A denotes the position of attachment tothe methylene moiety —CR⁵R⁶—.
 9. A compound according to claim 8,wherein Q is a group Q₁, Q₂, Q₅, Q₆, Q₇, Q₂₅, Q₂₆, Q₂₇, Q₂₈, Q₂₉, Q₃₄,Q₄₂ or Q₄₃.
 10. A compound according to claim 8, wherein R is methyl orethyl.
 11. A compound according to claim 8, wherein n is 0, 1 or
 2. 12.A compound according to claim 1, wherein R¹ is methyl, ethyl or methoxy,R² and R³ are independently hydrogen, halogen, C₁-C₆alkyl, phenyl,phenyl substituted by C₁-C₄alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,C₁-C₃alkoxy-C₁-C₃alkoxy, C₁-C₃haloalkoxy, aminocarbonyl, cyano orhalogen, or phenyl wherein 2 adjacent carbon atoms are bridged by a—O—CH₂—O— or —O—CH₂—CH₂—O— group, or heteroaryl or heteroarylsubstituted by C₁-C₃alkoxy or cyclopropyl-C₁-C₃alkoxy, R⁴ is hydrogen,methyl or ethyl, R⁵ is hydrogen, R⁶ and R⁷ are independently hydrogen ormethyl, and Q is a 5- to 7-membered saturated heterocycle containing atleast one heteroatom selected from O and S(O)_(p), or Q is a 5- to7-membered saturated or mono-unsaturated heterocycle containing at leastone heteroatom selected from O and S(O)_(p), which is substituted byC₁-C₄alkyl or C₁-C₄alkoxy-C₁-C₂alkyl, or is substituted by a 5- to6-membered heterocycyl containing at least one O atom, or is substitutedby a 5- to 6-membered heterocyclyl-C₁-C₃alkyl containing at least one Oatom, or is substituted by a spiro-C₃-C₆cycloalkyl or a spiro-5- to6-membered saturated heterocycle containing at least one O atom, or Q isa 8- to 10-membered bicyclic heterocycle containing at least one O atom,and p is 0, 1 or 2, and G is hydrogen.
 13. A process for the preparationof a compound of formula I according to claim 1, wherein G is hydrogen,which comprises reacting an iodonium ylide of Formula (AG),

wherein Ar is an optionally substituted phenyl group and R⁵, R⁶ and R⁷are as defined in claim 1, and an aryl boronic acid of Formula (AH)

wherein R¹ to R⁴ are as defined in claim 1, in the presence of apalladium catalyst, a base and in a solvent.
 14. A process for thepreparation of a compound of formula I according to claim 1, wherein Gis hydrogen, which comprises reacting a compound of formula (Q)

wherein R⁵ to R⁷ are as defined in claim 1, with a compound of formula(AR)

wherein R¹ to R⁴ are as defined in claim 1, in the presence of a ligandand in a solvent.
 15. A method of controlling grasses and weeds in cropsof useful plants, which comprises applying a herbicidally effectiveamount of a compound of formula I as defined in claim 1, or of acomposition comprising such a compound, to the plants or to the locusthereof.
 16. A herbicidal composition, which comprises a herbicidallyeffective amount of a compound of formula I as defined in claim 1, andoptionally a further herbicide as mixing partner or a safener or both.17. A compound according to claim 3, wherein R² and R³ are independentlyhydrogen, chlorine, bromine, methyl, methoxy, ethyl, ethoxy, ethenyl,ethynyl, phenyl or phenyl substituted by methyl, trifluoromethyl, cyano,nitro, fluorine, chlorine or methylsulfonyl.
 18. A compound according toclaim 1, wherein, when G is a latentiating group, then G is a group—C(X¹)—R⁶ or —C(X²)—X³—R⁷, and the meanings of X¹, R⁶, X², X³ and R⁷ areas defined in claim 1.